Curable resin composition, production method of image sensor chip using the same, and image sensor chip

ABSTRACT

There is provided a curable resin composition which is capable of being coated so as to have a film thickness of 20 μm or more and contains a dye having a maximum absorption wavelength in a wavelength range from 600 to 850 nm, and the infrared ray cut filter having a dye-containing layer having a film thickness of 20 μm or more formed from the curable resin composition, and a production method of image sensor chip comprising a step of coating the curable resin composition on a glass substrate to form a dye-containing layer, and a step of adhering the glass plate having the dye-containing layer formed on a solid-state imaging device substrate.

CROSS REFERENCE TO RELATED APPLICATION

This is a continuation of International Application No.PCT/JP2013/081980 filed on Nov. 27, 2013, and claims priority fromJapanese Patent Application No. 2012-263644 filed on Nov. 30, 2012, theentire disclosures of which are incorporated therein by reference.

TECHNICAL FIELD

The present invention relates to a curable resin composition, aproduction method of image sensor chip using the same, and an imagesensor chip.

BACKGROUND ART

A CCD or CMOS image sensor chip (hereinafter, simply referred to as an“image sensor chip”) which is a solid-state imaging device for colorimage is used in a video camera, a digital still camera, a cellularphone with camera function and the like. Since the solid-state imagingdevice uses a silicon photodiode having sensitivity to near infrared rayin the light receiving unit thereof, luminosity factor correction isrequired and an infrared ray cut filter is employed (for example, seePatent Document 1).

RELATED ART DOCUMENT Patent Document

Patent Document 1: JP-A-2012-28620

DISCLOSURE OF THE INVENTION Problems that the Invention is to Solve

However, when a surface of the solid-state imaging device substrate andthe infrared ray cut filter are faced with a space as described above,incident angle dependence of light which the solid-state imaging devicereceives increases to cause a problem of color shading in some cases.

The invention has been made in the light of the circumstances describedabove, and it is a problem of the invention to achieve the objectsdescribed below.

Specifically, an object of the invention is to provide a curable resincomposition capable of producing an image sensor chip in which the colorshading is suppressed.

Also, another object of the invention is to provide a curable resincomposition which can produce an image sensor chip in which a stackfunctioning as an infrared ray cut filter and including a layercontaining a dye having a maximum absorption wavelength in a wavelengthrange from 600 to 850 nm (hereinafter, also simply referred to as a“dye-containing layer”), an infrared ray reflecting film and the likeand a surface of a solid-state imaging device substrate are closelycontacted with each other without a space and by which the incidentangle dependence of light received can be suppressed, a productionmethod of image sensor chip using the same, and an image sensor chip.

Means for Solving the Problems

The invention has the configuration described below, and the objects ofthe invention described above are achieved thereby.

[1] A curable resin composition which is capable of being coated so asto have a film thickness of 20 μm or more and contains a dye having amaximum absorption wavelength in a wavelength range from 600 to 850 nm.

[2] The curable resin composition as described in [1],

wherein the dye is at least one kind selected from the group consistingof a pyrrolopyrrole dye, a copper complex, a cyanine-based dye, aphthalocyanine-based dye, a quaterrylene-based dye, an aminium-baseddye, an imminium-based dye, an azo-based dye, an anthraquinone-baseddye, a diimonium-based dye, a squarylium-based dye and a porphyrin-baseddye.

[3] The curable resin composition as described in [1],

wherein the dye is a pyrrolopyrrole dye or a copper complex.

[4] The curable resin composition as described in any one of [1] to [3],which has a solid content concentration from 10 to 90% by mass and aviscosity at 25° C. from 1 mPa·s to 1,000 Pa·s.[5] The curable resin composition as described in any one of [1] to [4],which further contains a polymerizable compound and a solvent, and acontent of the dye in a total solid content of the composition is 30% bymass or more.[6] A curable resin composition which contains a dye having a maximumabsorption wavelength in a wavelength range from 600 to 850 nm and has asolid content concentration from 10 to 90% by mass and a viscosity at25° C. from 1 mPa·s to 1,000 Pa·s.[7] An infrared ray cut filter having a dye-containing layer having afilm thickness of 20 μm or more formed from the curable resincomposition as described in any one of [1] to [6].[8] An infrared ray cut filter having a first dye-containing layercontaining a copper complex and a second dye-containing layer containinga pyrrolopyrrole dye.[9] The infrared ray cut filter as described in [8],

wherein a film thickness of the first dye-containing layer is 50 μm ormore and a film thickness of the second dye-containing layer is 5 μm orless.

[10] A production method of image sensor chip comprising a step ofcoating the curable resin composition as described in any one of [1] to[6] on a glass substrate to form a dye-containing layer, and a step ofadhering the glass plate having the dye-containing layer formed on asolid-state imaging device substrate.[11] The production method of image sensor chip as described in [10],

wherein the coating of the curable resin composition is applicatorcoating and the applicator coating is performed by setting a solidcontent concentration and a viscosity of the curable resin compositionto from 40 to 70% by mass and 300 to 700 mPa·s, respectively.

[12] The production method of image sensor chip as described in [10] or[11],

wherein the glass substrate further has an infrared ray reflecting film,and (1) a surface of the glass substrate on which the infrared rayreflecting film is formed is adhered on the solid-state imaging devicesubstrate or (2) a surface of the glass substrate on which the infraredray reflecting film is not formed is adhered on the solid-state imagingdevice substrate.

[13] The production method of image sensor chip as described in any oneof [10] to [12],

wherein the glass substrate further has an antireflection film.

[14] The production method of image sensor chip as described in [13],

wherein the infrared ray reflecting film is present on one surface ofthe glass substrate and the antireflection film is present on the othersurface of the glass substrate.

[15] The production method of image sensor chip as described in any oneof [12] to [14],

wherein the infrared ray reflecting film is a dielectric multilayerfilm.

[16] The production method of image sensor chip as described in any oneof [10] to [15],

wherein the solid-state imaging device substrate has a color filterlayer, a high refractive index layer and a low refractive index layer.

[17] An image sensor chip comprising a solid-state imaging devicesubstrate, a dye-containing layer composed of the curable resincomposition as described in any one of [1] to [6] and a glass substratehaving an infrared ray reflecting film, wherein these are closelycontacted with each other without intervention of an air layer.[18] The image sensor chip as described in [17],

wherein the infrared ray reflecting film is provided on a surface of theglass substrate opposed to the dye-containing layer composed of thecurable resin composition.

[19] The image sensor chip as described in [17],

wherein the dye-containing layer is provided between the infrared rayreflecting film and the glass substrate.

[20] The image sensor chip as described in any one of [17] to [19],

wherein an antireflection film is further provided on an outermostsurface of the image sensor chip comprising the solid-state imagingdevice substrate, the dye-containing layer and the infrared rayreflecting film.

Advantage of the Invention

According to the invention, a curable resin composition capable ofproducing an image sensor chip in which the color shading is suppressedcan be provided.

Also, a curable resin composition which can produce an image sensor chipin which a stack functioning as an infrared ray cut filter and includinga dye-containing layer, an infrared ray reflecting film and the like anda surface of a solid-state imaging device substrate are closelycontacted with each other without a space and by which the incidentangle dependence of light received can be suppressed, a productionmethod of image sensor chip using the same, and an image sensor chip canbe provided.

BRIEF DESCRIPTION OF THE DRAWING

FIG. 1 is a schematic cross-sectional view showing the configuration ofa camera module equipped with the solid-state imaging device accordingto an embodiment of the invention.

FIG. 2 is a schematic cross-sectional view of the solid-state imagingdevice substrate according to an embodiment of the invention.

FIG. 3A and FIG. 3B are schematic cross-sectional views showing anembodiment of the production method of image sensor chip according tothe invention.

MODE FOR CARRYING OUT THE INVENTION

The polymerizable composition according to the invention will bedescribed in detail hereinafter.

With respect to the description of a group (an atomic group) in thespecification, when the group is indicated without specifying whethersubstituted or unsubstituted, the group includes both a group having nosubstituent and a group having a substituent. For example, “an alkylgroup” includes not only an alkyl group having no substituent (anunsubstituted alkyl group) but also an alkyl group having a substituent(a substituted alkyl group). Also, in the specification, a viscosityvalue denotes a value at 25° C.

The curable resin composition according to the invention is capable ofbeing coated so as to have a film thickness of 20 μm or more andcontains a dye having a maximum absorption wavelength in a wavelengthrange from 600 to 850 nm.

The maximum absorption wavelength of the dye is based on a valueobtained by measuring a film having a film thickness of 1 μm obtained bycoating a solution prepared so as to have a content of the dye and aresin of 20% by mass based on the total solution using aspectrophotometer.

The curable resin composition according to the invention may be aheat-curable resin composition or a photocurable resin composition.

The solid-state imaging device substrate according to the inventionpreferably includes a color filter layer, a high refractive index layerand a low refractive index layer, as described later with reference toFIG. 1 and FIG. 2.

The constitution of the curable resin composition according to theinvention is described below.

The description of the constituent element below is made based on thetypical embodiment of the invention in some cases, but the inventionshould not be construed as being limited thereto. In the specification,a numerical value range represented by using the term “to” means a rangewhich includes the numerical values described before and after the term“to” as a lower limit and an upper limit, respectively.

In the specification, the term “(meth)acrylate” represents acrylate andmethacrylate, the term “(meth)acryl” represents acryl and methacryl, andthe term “(meth)acryloyl” represents acryloyl and methacryloyl. Also, inthe specification, the terms “monomer” and “monomer” have the samemeaning. The monomer in the invention is distinguished from an oligomerand a polymer and means a compound having a mass average molecularweight of 2,000 or less. In the specification, a polymerizable compoundmeans a compound having a polymerizable group and may be a monomer or apolymer. The polymerizable group means a group involved in apolymerization reaction.

[1] Dye having maximum absorption wavelength in wavelength range from600 to 850 nm

The dye which can be used in the invention is not particularly limitedso long as it has a maximum absorption wavelength (λmax) in a wavelengthrange from 600 to 850 nm and preferably includes, for example, at leastone kind selected from the group consisting of a pyrrolopyrrole dye, acopper complex, a cyanine-based dye, a phthalocyanine-based dye, aquaterrylene-based dye, an aminium-based dye, an imminium-based dye, anazo-based dye, an anthraquinone-based dye, a diimonium-based dye, asquarylium-based dye and a porphyrin-based dye. Among them, apyrrolopyrrole dye, a copper complex, a cyanine-based dye, aphthalocyanine-based dye or a quaterrylene-based dye is preferred, and apyrrolopyrrole dye, a copper complex, a cyanine-based dye or aphthalocyanine-based dye is more preferred.

As the dye, at least one kind selected from the group consisting of acyanine-based dye, a phthalocyanine-based dye, a quaterrylene-based dye,an aminium-based dye, an imminium-based dye, an azo-based dye, ananthraquinone-based dye, a diimonium-based dye, a squarylium-based dyeand a porphyrin-based dye is also one preferred embodiment.

By the way, in a soldering process in the production of electroniccomponent and the like used in a cellular phone and the like, aconventional process wherein a solder is molten to attach to a substratesurface has been replacing with a so-called a solder reflow process. Inthe solder reflow process, ordinarily, after mounting components havinga solder preliminarily printed on a substrate surface by means ofprinting or the like, soldering is performed in a reflow furnace. Thistechnique is advantageous in view of response to miniaturization of theelectronic component and productivity, and is effective in theproduction of camera module which is reduced in size and weight. In thecase of performing the solder reflow process, since the reflow furnaceis heated with hot air, a far infrared ray or the like, a membersubjected to the process is required to have heat resistance capable ofresponding to the reflow temperature.

From the above, in order to reduce the size and weight of camera moduleor the like, it is necessary to study the response to a so-calledreflowing wherein the production is accompanied with the solder flowprocess.

In particular, from the standpoint of the heat resistance endurable thereflow process, the pyrrolopyrrole dye and copper complex are preferred.

When the maximum absorption wavelength is less than 600 nm or when themaximum absorption wavelength is more than 850 nm, the shieldingproperty to a near infrared ray having a wavelength around 700 nm is lowso that a satisfactory result cannot be obtained.

The maximum absorption wavelength of the dye for use in the invention ispreferably in a range from 600 to 800 nm, more preferably in a rangefrom 640 to 770 nm, and particularly preferably in a range from 660 to720 nm.

As the pyrrolopyrrole dye, a compound represented by formula (A1) shownbelow is more preferred.

Formula (A1)

In formula (A1), R^(1a) and R^(1b) each independently represents analkyl group, an aryl group or a heteroaryl group. R² and R³ eachindependently represents a hydrogen atom or a substituent, and at leastone of R² and R³ is an electron withdrawing group, or R² and R³ may becombined with each other to form a ring. R⁴ represents a hydrogen atom,an alkyl group, an aryl group, a heteroaryl group, a substituted boronor a metal atom, or R⁴ may be covalently connected or coordinatelyconnected with at least one of R^(1a), R^(1b) and R³.

In formula (A1), the alkyl group represented by each of R^(1a) andR^(1b) is preferably an alkyl group having from 1 to 30 carbon atoms,more preferably an alkyl group having from 1 to 20 carbon atoms, andparticularly preferably an alkyl group having from 1 to 10 carbon atoms.

The aryl group represented by each of R^(1a) and R^(1b) is preferably anaryl group having from 6 to 30 carbon atoms, more preferably an arylgroup having from 6 to 20 carbon atoms, and particularly preferably anaryl group having from 6 to 12 carbon atoms.

The heteroaryl group represented by each of R^(1a) and R^(1b) ispreferably a heteroaryl group having from 1 to 30 carbon atoms, and morepreferably a heteroaryl group having from 1 to 12 carbon atoms. As thehetero atom, for example, a nitrogen atom, an oxygen atom and a sulfuratom are exemplified.

In particular, as the group represented by each of R^(1a) and R^(1b), anaryl group having an alkoxy group having a branched alkyl group ispreferred. The alkyl group in the branched alkyl group preferably hasfrom 3 to 30 carbon atoms, and more preferably has from 3 to 20 carbonatoms.

As the group represented by each of R^(1a) and R^(1b), for example,4-(2-ethylhexyloxyl)phenyl, 4-(2-methylbutyloxyl)phenyl or4-(2-octyldodecyloxyl)phenyl is particularly preferred. In formula (A1),R^(1a) and R^(1b) may be the same or different from each other.

R² and R³ each independently represents a hydrogen atom or a substituentT, and at least one of R² and R³ is an electron withdrawing group, or R²and R³ may be combined with each other to form a ring. In particular, R²and R³ each independently preferably represents a cyano group or aheterocyclic group.

The substituent T includes, for example, those described below.

An alkyl group (preferably having from 1 to 30 carbon atoms), an alkenylgroup (preferably having from 2 to 30 carbon atoms), an alkynyl group(preferably having from 2 to 30 carbon atoms), an aryl group (preferablyhaving from 6 to 30 carbon atoms), an amino group (preferably havingfrom 0 to 30 carbon atoms), an alkoxy group (preferably having from 1 to30 carbon atoms), an aryloxy group (preferably having from 6 to 30carbon atoms), an aromatic heterocyclic oxy group (preferably havingfrom 1 to 30 carbon atoms), an acyl group (preferably having from 1 to30 carbon atoms), an alkoxycarbonyl group (preferably having from 2 to30 carbon atoms), an aryloxycarbonyl group (preferably having from 7 to30 carbon atoms), an acyloxy group (preferably having from 2 to 30carbon atoms), an acylamino group (preferably having from 2 to 30 carbonatoms), an alkoxycarbonylamino group (preferably having from 2 to 30carbon atoms), an aryloxycarboylamino group (preferably having from 7 to30 carbon atoms), a sulfonylamino group (preferably having from 1 to 30carbon atoms), a sulfamoyl group (preferably having from 0 to 30 carbonatoms), a carbamoyl group (preferably having from 1 to 30 carbon atoms),an alkylthio group (preferably having from 1 to 30 carbon atoms), anarylthio group (preferably having from 6 to 30 carbon atoms), anaromatic heterocyclic thio group (preferably having from 1 to 30 carbonatoms), a sulfonyl group (preferably having from 1 to 30 carbon atoms),a sulfinyl group (preferably having from 1 to 30 carbon atoms), a ureidogroup (preferably having from 1 to 30 carbon atoms), a phosphoramidogroup (preferably having from 1 to 30 carbon atoms), a hydroxy group, amercapto group, a halogen atom, a cyano group, a sulfo group, a carboxylgroup, a nitro group, a hydroxamic acid group, a sulfino group, ahydrazino group, an imino group and a heterocyclic group (preferablyhaving from 1 to 30 carbon atoms).

Among R² and R³, at least one of R² and R³ is an electron withdrawinggroup. A substituent having a positive Hammett's σp value (sigma paravalue) ordinarily functions as an electron withdrawing group. Examplesof the electron withdrawing group include a cyano group, an acyl group,an alkyloxycarbonyl group, an aryloxycarbonyl group, a sulfamoyl group,a sulfinyl group and a heterocyclic group, and a cyano group is morepreferred. The electron withdrawing group may be further substituted.

According to the invention, a substituent having a Hammett's substituentconstant σp value of at least 0.2 or more can be exemplified as anelectron withdrawing group. The σ_(p) value is preferably 0.25 or more,more preferably 0.3 or more, and particularly preferably 0.35 or more.The upper limit thereof is not particularly limited, and is preferably0.80.

Specific examples thereof include a cyano group (0.66), a carboxyl group(—COOH: 0.45), an alkoxycarbonyl group (—COOMe: 0.45), anaryloxycarbonyl group (—COOPh: 0.44), a carbamoyl group (—CONH₂: 0.36),an alkylcarbonyl group (—COMe: 0.50), an arylcarbonyl group (—COPh:0.43), an alkylsulfonyl group (—SO₂Me: 0.72) and an arylsulfonyl group(—SO₂Ph: 0.68). A cyano group is particularly preferred. In the above,Me represents a methyl group and Ph represents a phenyl group.

The Hammett's substituent constant σ value can refer to, for example,paragraphs 0017 to 0018 of JP-A-2011-68731, and the contents thereof areincorporated into the specification.

In the case where R² and R³ are combined with each other to form a ring,it is preferred to from a 5-membered to 7-membered ring (preferably a5-membered or 6-membered ring). As the ring formed, a ring which isordinarily used as an acidic nucleus in a merocyanine dye is preferred,and specific examples thereof can refer to, for example, paragraphs 0019to 0021 of JP-A-2011-68731, and the contents thereof are incorporatedinto the specification.

R³ is particularly preferably a hetero ring. In particular, R³ ispreferably quinoline, benzothiazole or naphthothiazole.

In formula (A1), two groups represented by R² may be the same ordifferent from each other, and two groups represented by R³ may be thesame or different from each other.

In the case where the group represented by R⁴ is the alkyl group, thearyl group or the heteroaryl group, these groups have the same meaningsas those described for R^(1a) and R^(1b), respectively and preferredgroups are also the same.

In the case where the group represented by R⁴ is the substituted boron,the substituent has the same meaning as the substituent T described forR² and R³, and is preferably an alkyl group, an aryl group or aheteroaryl group.

In the case where the group represented by R⁴ is the metal atom, themetal atom is preferably a transition metal, particularly preferably asubstituted boron. As the substituted boron, difluoro boron, diphenylboron, dibutyl boron, dinaphthyl boron and catechol boron are preferablyexemplified. Among them, diphenyl boron is particularly preferred.

R⁴ may be covalently connected or coordinately connected with at leastone of R^(1a), R^(1b) and R³, and it is particularly preferred that R⁴is coordinately connected with R³.

In particular, R⁴ is preferably a hydrogen atom or a substituted boron(particularly diphenyl boron).

In formula (A1), two groups represented by R⁴ may be the same ordifferent from each other.

The compound represented by formula (A1) can refer to, for example,paragraphs 0024 to 0052 of JP-A-2011-68731 (corresponding to paragraphs0043 to 0074 of U.S. Patent Publication No. 2011/0070407), and thecontents thereof are incorporated into the specification.

As the pyrrolopyrrole dye, a compound represented by formula (A2) shownbelow is more preferred, and a compound represented by formula (A3)shown below is still more preferred. Formula (A2)

In formula (A2), R¹⁰ each independently represents a hydrogen atom, analkyl group, an aryl group, a heteroaryl group, a substituted boron or ametal atom, or R¹⁰ may be covalently connected or coordinately connectedwith R¹². R¹¹ and R¹² each independently represents a hydrogen atom or asubstituent, and at least one of R¹¹ and R¹² is an electron withdrawinggroup, or R¹¹ and R¹² may be combined with each other to form a ring.R¹³ each independently represents a branched alkyl group having from 3to 30 carbon atoms.

R¹⁰ has the same meanings as R⁴ in formula (A1) above, and preferredranges are also the same.

R¹¹ and R¹² have the same meanings as R² and R³ in formula (A1) above,and preferred ranges are also the same.

R¹³ may be the same or different from each other.

Also, R¹³ is preferably an alcohol residue derived, for example, fromisoeicosanol (FINEOXOCOL 2000 produced by Nissan Chemical Industries,Ltd.).

The alcohol may be straight-chain or branched and is preferably analcohol having from 1 to 30 carbon atoms, more preferably an alcoholhaving from 3 to 25 carbon atoms, and particularly preferably a branchedalcohol having from 3 to 25 carbon atoms. More specifically, methanol,ethanol, isopropanol, n-butanol, tert-butanol, 1-octanol, 1-decanol,1-hexadecanol, 2-methylbutanol, 2-ethylhexanol, 2-octyldodecanol,isohexadecanol (FINEOXOCOL 1600 produced by Nissan Chemical Industries,Ltd.), isooctadecanol (FINEOXOCOL 180 produced by Nissan ChemicalIndustries, Ltd.), isooctadecanol (FINEOXOCOL 180N produced by NissanChemical Industries, Ltd.), isooctadecanol (FINEOXOCOL 180T produced byNissan Chemical Industries, Ltd.), isoeicosanol (FINEOXOCOL 2000produced by Nissan Chemical Industries, Ltd.) and the like areexemplified. The alcohol may be a mixture of two or more thereof.

Formula (A3)

In formula (A3), R²⁰ each independently represents a branched alkylgroup having from 3 to 30 carbon atoms.

In formula (3A), R²⁰ has the same meanings as R¹³ in formula (A2) above,and preferred ranges are also the same.

In the case where the dye is the copper complex, the ligand Lcoordinated to the copper is not particularly limited so long as it isable to coordinate with a copper ion, and includes, for example, acompound having sulfonic acid, carboxylic acid, phosphoric acid, aphosphoric acid ester, phosphonic acid, a phosphonic acid ester,phosphinic acid, a substituted phosphinic acid, a carbonyl (ester,ketone), an amine, an amide, a sulfonamide, a urethane, a urea, analcohol, a thiol or the like.

Specific examples of the copper complex include a phosphorus-containingcopper compound, a copper sulfonate compound and a copper compoundrepresented by formula (B) shown below. The phosphorus-containing coppercompound specifically can refer to, for example, compounds describedfrom line 27 on page 5 to line 20 on page 7 of WO 2005/030898, and thecontents thereof are incorporated into the specification.

As the copper complex, for example, a copper complex represented byformula (B) shown below is exemplified.

Cu(X)_(n1)  Formula (B)

In formula (B), X represents a ligand coordinated to the copper, and n1each independently represents an integer from 1 to 6.

The ligand X includes a ligand having a substituent containing C, N, Oor S as an atom capable of coordinating to the copper, and is morepreferably a ligand including a group having a lone pair, for example,N, O or S. The group capable of coordinating is not limited to one kindin the molecule, two or more kinds thereof may be incorporated, and itmay be dissociated or non-dissociated.

The copper complex is a copper compound in which ligands are coordinatedto the copper as the central metal, and the copper is ordinarily adivalent copper. The copper complex can be obtained, for example, bymixing, reacting and the like a compound for forming the ligand or asalt thereof with a copper component.

The compound for forming the ligand or a salt thereof is notparticularly limited, and preferably includes, for example, an organicacid compound (for example, a sulfonic acid compound or a carboxylicacid compound) and a salt thereof.

In particular, a sulfonic acid compound represented by formula (J) shownbelow or a salt thereof is preferred.

Formula (J)

In formula (J), R⁷ represents a monovalent organic group.

Specifically, the monovalent organic group is not particularly limited,and includes, for example, a straight-chain, branched or cyclic alkylgroup, an alkenyl group and an aryl group. These groups may beintervened by a divalent connecting group (for example, an alkylenegroup, a cycloalkylene group, an arylene group, —O—, —S—, —CO—,—C(═O)O—, —OCO—, —SO₂— or —NR— (wherein R represents a hydrogen atom oran alkyl group). The monovalent organic group may have a substituent.

The straight-chain or branched alkyl group is preferably an alkyl grouphaving from 1 to 20 carbon atoms, more preferably an alkyl group havingfrom 1 to 12 carbon atoms, and still more preferably an alkyl grouphaving from 1 to 8 carbon atoms.

The cyclic alkyl group may be monocyclic or polycyclic. The cyclic alkylgroup is preferably a cycloalkyl group having from 3 to 20 carbon atoms,more preferably a cycloalkyl group having from 4 to 10 carbon atoms, andstill more preferably a cycloalkyl group having from 6 to 10 carbonatoms. The alkenyl group is preferably an alkenyl group having from 2 to10 carbon atoms, more preferably an alkenyl group having from 2 to 8carbon atoms, and still more preferably an alkenyl group having from 2to 4 carbon atoms.

The aryl group is preferably an aryl group having from 6 to 18 carbonatoms, more preferably an aryl group having from 6 to 14 carbon atoms,and still more preferably an aryl group having from 6 to 10 carbonatoms.

The alkylene group, cycloalkylene group and arylene group as thedivalent connecting group include divalent connecting groups derived byeliminating one hydrogen atom from the alkyl group, the cycloalkyl groupand the aryl group described above, respectively.

The substituent which the monovalent organic group may have includes analkyl group, a polymerizable group (for example, a vinyl group, a(meth)acryloyl group, an epoxy group or an oxetane group), a halogenatom, a carboxyl group, a carboxylic ester group (for example, —CO₂CH₃),a hydroxy group, an amido group and a halogenated alkyl group (forexample, a fluoroalkyl group or a chloroalkyl group).

The molecular weight of the sulfonic acid compound represented byformula (J) or the salt thereof is preferably from 80 to 750, morepreferably from 80 to 600, and still more preferably from 80 to 450.

Specific examples of the sulfonic acid compound represented by formula(J) are set forth below, but the invention should not be construed asbeing limited thereto.

The sulfonic acid compound can be used a commercially available sulfonicacid compound or can be synthesized with reference to a known method.The salt of the sulfonic acid compound includes, for example, a metalsalt, and specifically includes, for example, a sodium salt and apotassium salt.

As another copper complex, a copper complex containing a carboxylic acidas the ligand other than those described above. For example, a coppercomplex containing a compound represented by formula (K) shown below asthe ligand can be used.

Formula (K)

In formula (K), R¹ represents a monovalent organic group.

In formula (K), R¹ represents a monovalent organic group. The monovalentorganic group is not particularly limited, and, for example, has thesame meaning as the monovalent organic group in formula (J) describedabove.

<Copper Complex (Polymer Type)>

The copper complex may be a copper complex obtained by a reactionbetween a copper component and a polymer compound having a repeatingunit represented by formula (II) shown below or a salt thereof(hereinafter, also simply referred to as a “compound represented byformula (II)”).

The copper component is not particularly limited so long as it iscapable of forming a compound exhibiting a near infrared ray absorbingproperty by reacting with the compound represented by formula (II) shownbelow, and preferably includes copper hydroxide, copper acetate andcopper sulfate.

(Polymer compound having repeating unit represented by formula (II)shown below or salt thereof)

The polymer compound or salt thereof, which is reacted with the coppercomponent, has a repeating unit represented by formula (II) shown below.

In formula (II), R² represents an organic group, Y¹ represents a singlebond or a divalent connecting group, and X² represents an acid group.

In formula (II), R² is preferably a group containing an aliphatichydrocarbon group, an aromatic hydrocarbon group and/or an aromaticheterocyclic group.

In formula (II), in the case where Y¹ represents a divalent connectinggroup, the divalent connecting group includes a divalent hydrocarbongroup, a heteroarylene group, —O—, —S—, —CO—, —COO—, —OCO—, —SO₂—, —NX—(wherein X represents a hydrogen atom or an alkyl group, and ispreferably a hydrogen atom), and a group formed by a combination ofthese groups.

The divalent hydrocarbon group includes a straight-chain, branched orcyclic alkylene group and an arylene group. Although the hydrocarbongroup may have a substituent, it is preferred to be unsubstituted.

The carbon number of the straight-chain alkylene group is preferablyfrom 1 to 30, more preferably from 1 to 15, and still more preferablyfrom 1 to 6. The carbon number of the branched alkylene group ispreferably from 3 to 30, more preferably from 3 to 15, and still morepreferably from 3 to 6. The cyclic alkylene group may be monocyclic orpolycyclic. The carbon number of the cyclic alkylene group is preferablyfrom 3 to 20, more preferably from 4 to 10, and still more preferablyfrom 6 to 10.

The carbon number of the arylene group is preferably from 6 to 18, morepreferably from 6 to 14, and still more preferably from 6 to 10. Aphenylene group is particularly preferred as the arylene group.

The heteroarylene group is preferably a 5-membered ring or a 6-memberedring. The heteroarylene group may be monocyclic or polycyclic, and ispreferably monocyclic or a condensed ring having from 2 to 8 rings, andmore preferably monocyclic or a condensed ring having from 2 to 4 rings.

In formula (II), X² represents an acid group, and is preferably acarboxylic acid group or a sulfonic acid group, and more preferably asulfonic acid group.

According to a first embodiment of the compound represented by formula(II), the polymer compound is a polymer containing a carbon-carbon bondin the main chain thereof, and preferably contains a repeating unitrepresented by formula (II-1A) shown below, and more preferably containsa repeating unit represented by formula (II-1B) shown below.

In formula (II-1A), R¹ represents a hydrogen atom or a methyl group, L¹represents a single bond or a divalent connecting group, and X¹represents an acid group.

In formula (II-1B), R² represents a hydrogen atom or a methyl group, L²represents a divalent connecting group, and M¹ represents a hydrogenatom or an atom or atomic group constituting a salt with the sulfonicacid group.

In formula (II-1A) and formula (II-1B), R¹ and R² each independentlypreferably represents a hydrogen atom.

In the case where L¹ and L² each represents a divalent connecting groupin formula (II-1A) and formula (II-1B), the divalent connecting grouphas the same meaning as the divalent connecting group represented by Y¹described above, and preferred ranges are also the same.

In formula (II-1A), X¹ has the same meaning as X² in formula (II) above,and preferred ranges are also the same.

In formula (II-1B), M¹ is preferably a hydrogen atom.

The compounds represented by formula (II) may contain other repeatingunit than the repeating unit represented by formula (II-1A) or therepeating unit represented by formula (II-1B). As to the other repeatingunit, the description of copolymerization component disclosed inparagraphs 0068 to 0075 of JP-A-2010-106268 (corresponding to paragraphs0112 to 0118 of U.S. Patent Publication No. 2011/0124824) can bereferred to, and the contents thereof are incorporated into thespecification.

Preferred other repeating unit includes a repeating unit represented byformula (II-1C) shown below.

In formula (II-1C), R³ represents a hydrogen atom or a methyl group, andis preferably a hydrogen atom.

Y² represents a single bond or a divalent connecting group, and thedivalent connecting group has the same meaning as the divalentconnecting group represented by Y¹ described above. In particular, Y² ispreferably —COO—, —CO—, —HN—, a straight-chain or branched alkylenegroup, a group formed by a combination of these groups, or a singlebond.

In formula (II-1C), X² represents —PO₃H, —PO₃H₂, —OH or —COOH, and ispreferably —COOH.

In the case where the compound represented by formula (II) containsother repeating unit (preferably the repeating unit represented byformula (II-1A) or formula (II-1B), a molar ratio of the repeating unitrepresented by formula (II-1A) or formula (II-1B) and the repeating unitrepresented by formula (II-1C) is preferably from 95:5 to 20:80, andmore preferably from 90:10 to 40:60.

Specific examples of the first embodiment of the compound represented byformula (II) include the compounds set forth below and salts thereof,but the invention should not be construed as being limited thereto.

TABLE 1 B-1 

  Mw = 100000 B-2 

  Mw = 20000 B-3 

  Mw = 50000 B-4 

  a/b = 80/20 mol % Mw = 40000 B-5 

  a/b = 90/10 mol % Mw = 45000 B-6 

  Mw = 5,000 B-7 

  Mw = 20,000 B-8 

  Mw = 100,000 B-9 

  Mw = 30,000 B-10

  Mw = 30,000 B-11

  Mw = 30,000 B-12

  Mw = 30,000 B-13

  Mw = 30,000 B-14

  Mw = 20,000 B-15

  Mw = 20,000

Specific examples of the cyanine-based dye and the quaterrylene-baseddye includes compounds described, for example, in JP-A-2012-215806 andJP-A-2008-9206.

Specific examples of the phthalocyanine compound include compoundsdescribed in JP-A-60-224589, JP-T-2005-537319, JP-A-4-23868,JP-A-4-39361, JP-A-5-78364, JP-A-5-222047, JP-A-5-222301, JP-A-5-222302,JP-A-5-345861, JP-A-6-25548, JP-A-6-107663, JP-A-6-192584,JP-A-6-228533, JP-A-7-118551, JP-A-7-118552, JP-A-8-120186,JP-A-8-225751, JP-A-9-202860, JP-A-10-120927, JP-A-10-182995,JP-A-11-35838, JP-A-2000-26748, JP-A-2000-63691, JP-A-2001-106689,JP-A-2004-18561, JP-A-2005-220060 and JP-A-2007-169343.

Specific examples of the azo dye, the anthraquinone dye (anthraquinonecompound) and the squarylium-based dye (squarylium compound) includescompounds described, for example, in JP-A-2012-215806.

The dye is also available as a commercial product, and for example,LUMOGEN IR765 and LUMOGEN IR788 (produced by BASF), ABS643, ABS654,ABS667, ABS670T, IRA693N and IRA735 (produced by Exciton, Inc.),SDA3598, SDA6075, SDA8030, SDA8303, SDA8470, SDA3039, SDA3040, SDA3922and SDA7257 (produced by H.W. Sands Corp.) and TAP-15 and IR-706(produced by Yamada Chemical Co., Ltd.) are exemplified, and inparticular, as the cyanine dye Daito Chmix 1371F (produced by DaitoChemix Corp.), and as phthalocyanine dye EXCOLOR Series, EXCOLOR TX-EX720 and EXCOLOR TX-EX 708K (produced by Nippon Shokubai Co., Ltd.) andthe like are exemplified, but the invention should not be construed asbeing limited thereto.

The dye is preferably a fine particle. The average particle size of thedye is preferably 800 nm or less, more preferably 400 nm or less, andstill more preferably 200 nm or less. By setting the average particlesize in the range described above, since the dye is less likely to blockthe visible light by light scattering, it is possible to more ensure alight transmitting property in the visible light region. From thestandpoint of avoiding the light scattering, the smaller averageparticle size is preferred, but because of the ease of handling at thetime of production and the like, the average particle size of the dye isordinarily 1 nm or more.

The content of the dye is preferably from 0.05 to 90% by mass, morepreferably from 0.5 to 80% by mass, based on the total solid contentmass of the composition according to the invention.

However, in the case where the dye is the copper complex, the content ofthe copper complex is preferably 30% by mass or more, more preferablyfrom 30 to 90% by mass, still more preferably from 40 to 90% by mass,particularly preferably from 50 to 90% by mass, based on the total solidcontent mass of the composition according to the invention.

In particular, it is one preferred embodiment of the invention that thecomposition according to the invention further contains a polymerizablecompound and a solvent described later and the content of the dye in thetotal solid content of the composition is 30% by mass or more.

In the case where the dye has high c (epsilon), the content thereof maybe small, but in the case where the dye has low c (epsilon), the contentthereof becomes large. In the case where the dye is the cyanine-baseddye, phthalocyanine-based dye or the like, the content of the dye ispreferably from 0.01 to 20% by mass, more preferably from 0.5 to 10% bymass, based on the total solid content mass of the composition accordingto the invention.

Also, two or more kinds of the dyes may be used. For example, it ispreferred to use the pyrrolopyrrole dye and the copper complex incombination from the standpoint of the heat resistance endurable thereflow process. In the case of using two or more kinds of dyes, the dyesmay be incorporated into the same layer or may be incorporated intodifferent layers.

[2] Polymerizable Compound

The curable resin composition according to the invention can bepreferably constituted by containing at least one kind of polymerizablecompounds.

As the polymerizable compound, a compound having two or more epoxygroups or oxetanyl groups in its molecule is preferably used.

(Compound Having Two or More Epoxy Groups (Oxiranyl Groups) or OxetanylGroups in its Molecule)

Specific examples of the compound having two or more epoxy groups in itsmolecule as the polymerizable compound include a bisphenol A type epoxyresin, a bisphenol F type epoxy resin, a phenol novolac type epoxyresin, a cresol novolac type epoxy resin, and an aliphatic epoxy resin.

These are available as commercial products. For instance, as thebisphenol A type epoxy resin, for example, JER-827, JER-828, JER-834,JER-1001, JER-1002, JER-1003, JER-1055, JER-1007, JER-1009 and JER-1010(produced by Mitsubishi Chemical Corp.), and EPICLON 860, EPICLON 1050,EPICLON 1051 and EPICLON 1055 (produced by DIC Corp.) are exemplified,as the bisphenol F type epoxy resin, JER-806, JER-807, JER-4004,JER-4005, JER-4007, JER-4010 (produced by Mitsubishi Chemical Corp.),EPICLON 830 and EPICLON 835 (produced by DIC Corp.), and LCE-21 andRE-6025 (produced by Nippon Kayaku Co., Ltd.) are exemplified, as thephenol novolak type epoxy resin, JER-152, JER-154, JER-157570 andJER-157565 (produced by Mitsubishi Chemical Corp.), and EPICLON N-740,EPICLON N-740, EPICLON N-770 and EPICLON N-775 (produced by DIC Corp.)are exemplified, as the cresol novolak epoxy resin, EPICLON N-660,EPICLON N-665, EPICLON N-670, EPICLON N-673, EPICLON N-680, EPICLONN-690 and EPICLON N-695 (produced by DIC Corp.), and EOCN-1020 (producedby Nippon Kayaku Co., Ltd.) are exemplified, and as the aliphatic epoxyresin, ADEKA RESIN EP-4080S, ADEKA RESIN EP-4085S and ADEKA RESINEP-4088S (produced by ADEKA Corp.), CELLOXIDE 2021P, CELLOXIDE 2081,CELLOXIDE 2083, CELLOXIDE 2085, EHPE-3150, EPOLEAD PB 3600 and EPOLEADPB 4700 (produced by Daicel Chemical Industries, Ltd.), and DENACOLEX-211L, EX-212L, EX-214L, EX-216L, EX-321L and EX-850L (produced byNagase chemteX Corp.) are exemplified. In addition, ADEKA RESINEP-4000S, ADEKA RESIN EP-4003S, ADEKA RESIN EP-4010S and ADEKA RESINEP-4011S (produced by ADEKA Corp.), NC-2000, NC-3000, NC-7300, XD-1000,EPPN-501 and EPPN-502 (produced by ADEKA Corp.), JER-10315 (produced byMitsubishi Chemical Corp.) and the like are exemplified.

The compounds may be used individually or in combination of two or morethereof.

Specific examples of the compound having two or more oxetanyl groups inits molecule include ARONOXETAN OXT-121, OXT-221, OX-SQ and PNOX(produced by Toagosei Co., Ltd.).

Also, the compound containing oxetanyl groups is preferably usedindividually or in combination with the compound containing epoxygroups.

The polymerizable compound is also preferably selected from compoundshaving at least one terminal ethylenically unsaturated bond, preferablytwo or more terminal ethylenically unsaturated bonds. The polymerizablecompound may be used individually or in combination of two or morethereof in the invention. In particular, any of the compound having twoor more epoxy groups or oxetanyl groups in its molecule and the compoundhaving at least one terminal ethylenically unsaturated bond, preferablytwo or more terminal ethylenically unsaturated bonds may be usedindividually, or the compound having two or more epoxy groups oroxetanyl groups in its molecule and the compound having at least oneterminal ethylenically unsaturated bond, preferably two or more terminalethylenically unsaturated bonds may be used in combination.

As to the compound having at least one terminal ethylenicallyunsaturated bond, preferably two or more terminal ethylenicallyunsaturated bonds, specifically, examples of the monomer and prepolymerthereof include an unsaturated carboxylic acid (for example, acrylicacid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acidor maleic acid), its esters and its amides, and multimers thereof.Esters of an unsaturated carboxylic acid and an aliphatic polyhydricalcohol compound, amides of an unsaturated carboxylic acid and analiphatic polyvalent amine compound, and multimers thereof arepreferred.

Also, an addition reaction product of an unsaturated carboxylic acidester or amide having a nucleophilic substituent, for example, a hydroxygroup, an amino group or a mercapto group, with a monofunctional orpolyfunctional isocyanate or epoxy compound, and a dehydrationcondensation reaction product of the unsaturated carboxylic acid esteror amide with a monofunctional or polyfunctional carboxylic acid may bealso preferably used.

Also, an addition reaction product of an unsaturated carboxylic acidester or amide having an electrophilic substituent, for example, anisocyanate group or an epoxy group, with a monofunctional orpolyfunctional alcohol, amine or thiol, and a substitution reactionproduct of an unsaturated carboxylic acid ester or amide having areleasable substituent, for example, a halogen atom or a tosyloxy group,with a monofunctional or polyfunctional alcohol, amine or thiol are alsopreferable.

As other examples, compounds where the unsaturated carboxylic aciddescribed above is replaced by an unsaturated phosphonic acid, avinylbenzene derivative, for example, styrene, vinyl ether, allyl ethermay also be used.

As to specific examples of the compound, compounds described inparagraphs 0095 to 0108 of JP-A-2009-288705 may also be preferably usedin the invention.

As to the polymerizable compound, a compound having at least oneaddition-polymerizable ethylene group and having a boiling point of 100°C. or more under normal pressure is also preferred as a polymerizablemonomer. Examples thereof include a monofunctional acrylate ormethacrylate, for example, polyethylene glycol mono(meth)acrylate,polypropylene glycol mono(meth)acrylate or phenoxyethyl (meth)acrylate;a polyfunctional acrylate or methacrylate, for example, polyethyleneglycol di(meth)acrylate, trimethylolethane tri(meth)acrylate, neopentylglycol di(meth)acrylate, pentaerythritol tri(meth)acrylate,pentaerythritol tetra(meth)acrylate, dipentaerythritolpenta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, hexanediol(meth)acrylate, trimethylolpropane tri(acryloyloxypropyl)ether,tri(acryloyloxyethyl) isocyanurate, a compound obtained by addingethylene oxide or propylene oxide to a polyfunctional alcohol, forexample, glycerol or trimethylolethane, followed by (meth)acrylation, anurethane (meth)acrylate as described in JP-B-48-41708, JP-B-50-6034 andJP-A-51-37193, a polyester acrylate described in JP-A-48-64183,JP-B-49-43191 and JP-B-52-30490, and an epoxy acrylate as a reactionproduct of an epoxy resin and (meth)acrylic acid; and a mixture thereof.

A polyfunctional (meth)acrylate obtained by reacting a polyfunctionalcarboxylic acid with a compound having a cyclic ether group and anethylenically unsaturated group, for example, glycidyl (meth)acrylate isalso exemplified.

As other preferred polymerizable compounds, compounds having a fluorenering and difunctional or more ethylenically unsaturated groups describedin JP-A-2010-160418, JP-A-2010-129825 and Japanese Patent No. 4364216,and a cardo resin may be also used.

Also, as the compound having a boiling point of 100° C. or more undernormal pressure and having at least one addition-polymerizableethylenically unsaturated group, compounds described in paragraphs 0254to 0257 of JP-A-2008-292970 are also preferable.

In addition, radical polymerizable monomers represented by formulae(MO-1) to (MO-5) described in paragraphs 0297 to 0300 ofJP-A-2012-215806 may also preferably used.

As specific examples of the radical polymerizable monomers representedby formulae (MO-1) to (MO-5), compounds described in paragraphs 0248 to0251 of JP-A-2007-269779 may also preferably used in the invention.

Compounds obtained by adding ethylene oxide or propylene oxide to theabove-described polyfunctional alcohol and then (meth)acrylating theadduct, described as formulae (1) and (2) together with their specificexamples in JP-A-10-62986 may also be used as the polymerizablecompound.

Among them, as the polymerizable compound, dipentaerythritol triacrylate(as a commercial product, KAYARAD D-330 produced by Nippon Kayaku Co.,Ltd.), dipentaerythritol tetraacrylate (as a commercial product, KAYARADD-320 produced by Nippon Kayaku Co., Ltd.), dipentaerythritolpenta(meth)acrylate (as a commercial product, KAYARAD D-310, produced byNippon Kayaku Co., Ltd.), dipentaerythritol hexa(meth)acrylate (as acommercial product, KAYARAD DPHA, produced by Nippon Kayaku Co., Ltd.),and structures where the (meth)acryloyl group of the compounds describedabove are connected through an ethylene glycol or propylene glycolresidue are preferred. Oligomer types of these compounds may also beused.

The polymerizable compound may be a polyfunctional compound having anacid group, for example, a carboxyl group, sulfonic acid group orphosphoric acid group. Therefore, an ethylenic compound having anunreacted carboxyl group as in the case of the mixture described abovemay be used as it is, but, if desired, a non-aromatic carboxylicanhydride may be reacted with a hydroxy group of the ethylenic compoundto introduce an acid group. In this case, specific examples of thenon-aromatic carboxylic anhydride include tetrahydrophthalic anhydride,an alkylated tetrahydrophthalic anhydride, hexahydrophthalic anhydride,an alkylated hexahydrophthalic anhydride, succinic anhydride and maleicanhydride.

In the invention, the acid group-containing monomer is preferably apolyfunctional monomer which is an ester of an aliphatic polyhydroxycompound and an unsaturated carboxylic acid and obtained by reacting anon-aromatic carboxylic anhydride with an unreacted hydroxyl group ofthe aliphatic polyhydroxy compound to introduce the acid group, andparticularly preferably the ester described above wherein the aliphaticpolyhydroxy compound is pentaerythritol and/or dipentaerythritol.Examples of the commercial product thereof include as a polybasicacid-modified acryl oligomer, M-305, M-510 and M-520 of ARONIX Seriesproduced by Toagosei Co., Ltd.

One of the monomers may be used alone, but since it is difficult to usea single compound in view of production, two or more monomers may beused as a mixture. Also, as the monomer, a polyfunctional monomer havingno acid group and an acid polyfunctional monomer having an acid groupmay be used in combination, if desired. The acid value of thepolyfunctional monomer having an acid group is preferably from 0.1 to 40mg-KOH/g, and particularly preferably from 5 to 30 mg-KOH/g. When theacid value of the polyfunctional monomer is too low, a developmentdissolution characteristic decreases, on the other hand, when it is toohigh, production and handling become difficult, a photopolymerizationcharacteristic decreases, and a curing property, for example, surfacesmoothness of the pixel deteriorates. Therefore, in the case where twoor more polyfunctional monomers having different acid groups are used incombination or where a polyfunctional monomer having no acid group isused in combination, it is essential to adjust the monomers such thatthe acid value as the total polyfunctional monomer falls within therange described above.

Also, as the polymerizable monomer, a polyfunctional monomer having acaprolactone structure described in described in paragraphs 0306 to 0313of JP-A-2012-215806 may be used.

The polyfunctional monomer having a caprolactone structure iscommercially available as KAYARAD DPCA Series from Nippon Kayaku Co.,Ltd., and includes DPCA-20 (compound represented by formulae (1) to (3)described above, wherein m is 1, a number of the group represented byformula (2) is 2, and all of R¹ are hydrogen atoms), DPCA-30 (compoundrepresented by formulae (1) to (3) described above, wherein m is 1, anumber of the group represented by formula (2) is 3, and all of R¹ arehydrogen atoms), DPCA-60 (compound represented by formulae (1) to (3)described above, wherein m is 1, a number of the group represented byformula (2) is 6, and all of R¹ are hydrogen atoms) and DPCA-120(compound represented by formulae (1) to (3) described above, wherein mis 2, a number of the group represented by formula (2) is 6, and all ofR¹ are hydrogen atoms).

The polyfunctional monomers having a caprolactone structure may be usedindividually or as a mixture of two or more thereof in the invention.

Also, as the polymerizable compound according to the invention,compounds represented by formula (Z-4) or (Z-5) described in paragraphs0314 to 0324 of JP-A-2012-215806 may be used.

Examples of commercial product of the polymerizable compoundsrepresented by formulae (Z-4) and (Z-5) include SR-494, which is atetrafunctional acrylate having four ethyleneoxy chains, produced bySartomer Co., and DPCA-60, which is a hexafunctional acrylate having sixpentyleneoxy chains and TPA-330, which is a trifunctional acrylatehaving three isobutyleneoxy chains, both produced by Nippon Kayaku Co.,Ltd.

Furthermore, urethane acrylates as described in JP-B-48-41708,JP-A-51-37193, JP-B-2-32293 and JP-B-2-16765, and urethane compoundshaving an ethylene oxide skeleton described in JP-B-58-49860,JP-B-56-17654, JP-B-62-39417 and JP-B-62-39418 are also preferable asthe polymerizable compound. In addition, by using as the polymerizablecompound, an addition-polymerizable compound having an amino structureor a sulfide structure in the molecule thereof described inJP-A-63-277653, JP-A-63-260909 and JP-A-1-105238, a curable compositionvery excellent in photosensitive speed can be obtained.

Examples of commercial product of the polymerizable compound includeurethane oligomers UAS-10 and UAB-140 (produced by Sanyo Kokusaku PulpCo., Ltd.), UA-7200 (produced by Shin-Nakamura Chemical Co., Ltd.),DPHA-40H (produced by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T,UA-3061, AH-600, T-600 and AI-600 (produced by Kyoeisha Chemical Co.,Ltd.).

As the polymerizable compound, a polyfunctional thiol compound havingtwo or more mercapto (SH) groups in its molecule described in paragraphs0216 to 0220 of JP-A-2012-150468 may also be used.

As to the polymerizable compound, details of the method of usingthereof, for example, the structure thereof, individual or combinationuse or the amount thereof added can be appropriately determined inaccordance with the final characteristic design of the curable resincomposition. For example, from the standpoint of the sensitivity, astructure having a large unsaturated group content per molecular ispreferred, and in many cases, a difunctional or higher functionalstructure is preferred. From the standpoint of increasing the strengthof infrared ray cut filter, a trifunctional or higher functionalcompound is preferred. Further, a method of using compounds havingdifferent numbers of functional groups or different polymerizable groups(for example, an acrylate, a methacrylate, a styrene-based compound or avinyl ether-based compound) in combination to control both thesensitivity and the strength is also effective. Moreover, the selectionand use method of the polymerizable compound are also important factorsfor the compatibility and dispersibility with other components (forexample, a dye, a photopolymerization initiator or a binder) containedin the curable resin composition. For example, the compatibility can besometimes improved by using a low-purity compound or using two or morekinds of compounds in combination. Also, a specific structure may beselected for the purpose of improving the adhesion property to a hardsurface of a support or the like.

The content of the polymerizable compound in the curable resincomposition according to the invention is preferably from 0.1 to 90% bymass, more preferably from 1.0 to 80% by mass, particularly preferablyfrom 2.0 to 70% by mass, based on the solid content of the curable resincomposition.

[3] Polymerization Initiator

The curable resin composition according to the invention may contain apolymerization initiator. The polymerization initiator is notparticularly limited so long as it has a function of initiatingpolymerization of the polymerizable compound by either light or heat orboth of them, and it can be appropriately selected according to thepurpose, but it is preferably a photopolymerizable compound. In the caseof initiating the polymerization by light, a compound havingphotosensitivity to light from an ultraviolet region to a visible regionis preferred.

In the case of initiating the polymerization by heat, an initiatorcapable of being decomposed from 150 to 250° C. is preferred.

The polymerization initiator which can be used in the invention ispreferably a compound having at least an aromatic group, and includes,for example, an acyl phosphine compound, an acetophenone-based compound,an α-aminoketone compound, a benzophenone-based compound, a benzoinether-based compound, a ketal derivative compound, a thioxanthonecompound, an oxime compound, a hexaarylbiimidazole compound, atrihalomethyl compound, an azo compound, an organic peroxide, adiazonium compound, an iodonium compound, a sulfonium compound, anazinium compound, a benzoin ether-based compound, a ketal derivativecompound, an onium salt compound, for example, a metallocene compound,an organic boron salt compound and a disulfone compound.

From the standpoint of the sensitivity, an oxime compound, anacetophenone-based compound, an α-aminoketone compound, a trihalomethylcompound, a hexaarylblimidazole compound and a thiol compound arepreferred.

Examples of the polymerization initiator preferable in the invention areset forth below, but the invention should not be construed as beinglimited thereto.

The acetophenone-based compound specifically includes, for example,2,2-diethoxyacetophenone, p-dimethylaminoacetophenone,2-hydroxy-2-methyl-1-phenylpropan-1-one, p-dimethylaminoacetophenone,4′-isopropyl-2-hydroxy-2-methylpropiophenone, 1-hydroxycyclohexyl phenylketone,2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butanone-1,2-tolyl-2-dimethylamino-1-(4-morpholinophenyl)butanone-1,2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropanone-1,2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one,2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butanone-1,2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanoneand 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one.

As the trihalomethyl compound, a s-triazine derivative having at leastone of mono-, di- or tri-halogen substituted methyl group connected tothe s-triazine ring is more preferable, and specifically includes, forexample, 2,4,6-tris(monochloromethyl)-s-triazine,2,4,6-tris(dichloromethyl)-s-triazine,2,4,6-tris(trichloromethyl)-s-triazine,2-methyl-4,6-bis(trichloromethyl)-s-triazine,2-n-propyl-4,6-bis(trichloromethyl)-s-triazine,2-(α,α,β-trichloroethyl)-4,6-bis(trichloromethyl)-s-triazine,2-phenyl-4,6-bis(trichloromethyl)-s-triazine,2-(p-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine,2-(3,4-epoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine,2-(p-chlorophenyl)-4,6-bis(trichloromethyl)-s-triazine,2-[1-(p-methoxyphenyl)-2,4-butadienyl]-4,6-bis(trichloromethyl)-s-triazine,2-styryl-4,6-bis(trichloromethyl)-s-triazine,2-(p-methoxystyryl)-4,6-bis(trichloromethyl)-s-triazine,2-(p-isopropyloxystyryl)-4,6-bis(trichloromethyl)-s-triazine,2-(p-tolyl)-4,6-bis(trichloromethyl)-s-triazine,2-(4-naphthoxynaphthyl)-4,6-bis(trichloromethyl)-s-triazine,2-phenylthio-4,6-bis(trichloromethyl)-s-triazine,2-benzylthio-4,6-bis(trichloromethyl)-s-triazine,2,4,6-tris(dibromomethyl)-s-triazine,2,4,6-tris(tribromomethyl)-s-triazine,2-methyl-4,6-bis(tribromomethyl)-s-triazine and2-methoxy-4,6-bis(tribromomethyl)-s-triazine.

The hexaarylbiimidazole compound includes various compounds described,for example, in JP-B-6-29285 and U.S. Pat. Nos. 3,479,185, 4,311,783 and4,622,286 and specifically, for example,2,2′-bis(o-chlorophenyl)-4,4′,5,5′-tetraphenylbiimidazole,2,2′-bis(o-bromophenyl)-4,4′,5,5′-tetraphenylbiimidazole,2,2′-bis(o,p-dichlorophenyl)-4,4′,5,5′-tetraphenylbiimidazole,2,2′-bis(o-chlorophenyl)-4,4′,5,5′-tetra(m-methoxyphenyl)biimidazole,2,2′-bis(o,o′-dichlorophenyl)-4,4′,5,5′-tetraphenylbiimidazole,2,2′-bis(o-nitrophenyl)-4,4′,5,5′-tetraphenylbiimidazole,2,2′-bis(o-methylphenyl)-4,4′,5,5′-tetraphenylbiimidazole and2,2′-bis(o-trifluorophenyl)-4,4′,5,5′-tetraphenylbiimidazole.

The oxime compound includes, for example, compounds described in J. C.S. Perkin II (1979) 1653-1660, J. C. S. Perkin II (1979) 156-162,Journal of Photopolymer Science and Technology (1995) 202-232 andJP-A-2000-66385, compounds described in JP-A-2000-80068 andJP-T-2004-534797, and IRGACURE OXE 01 (1,2-octanedione,1-[4-(phenylthio)-, 2-(O-benzoyl oxime)]), IRGACURE OXE 02 (ethanone,1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetyloxime))and 2-(acetyloxyiminomethyl)thioxanthen-9-one (produced by BASF JapanLtd.).

Further, cyclic oxime compounds described in JP-A-2007-231000 andJP-2007-322744 are also preferably used.

Most preferably, an oxime compound having a specific substituentdescribed in JP-A-2007-269779 or an oxime compound having a thioarylgroup described in JP-2009-191061 is exemplified.

The photopolymerization initiator is more preferably a compound selectedfrom the group consisting of an oxime compound, an acetophenone-basedcompound and an acyl phosphine compound. More specifically, for example,aminoacetophenone-based initiators described in JP-A-10-291969, acylphosphine oxide-based initiators described in Japanese Patent No.4225898, the oxime-based initiators described above, and as anoxime-based initiator, compounds described in JP-A-2001-233842 can beused.

As the acetophenone-based initiator, commercial products, that is,IRGACURE-907, IRGACURE-369 and IRGACURE-379 (trade names, produced byBASF Japan Ltd.) can be used. As the acyl phosphine-based initiator,commercial products, that is, IRGACURE-819 or DAROCUR-TPO (trade names,produced by BASF Japan Ltd.) can be used.

The polymerization initiator may be used individually or may be used incombination of two or more thereof.

The content of polymerization initiator is preferably from 0.01 to 30%by mass, more preferably from 0.1 to 20% by mass, particularlypreferably from 0.1 to 15% by mass, with respect to the total solidcontent mass of the polymerizable composition according to theinvention.

[4] Binder

The curable resin composition according to the invention may contain abinder.

The binder is not particularly limited, and it may be an alkali-solubleresin.

The alkali-soluble resin can be appropriately selected fromalkali-soluble resins each of which is a liner organic high molecularpolymer and contains at least one group accelerating alkali-solubilityin its molecule (preferably, molecule in which a main chain is anacrylic copolymer or a styrene copolymer). From the standpoint of heatresistance, a polyhydroxystyrene-based resin, a polysiloxane-basedresin, an acrylic resin, an acrylamide-based resin and anacrylic/acrylamide copolymer resin are preferred, and from thestandpoint of controlling development property, an acrylic resin, anacrylamide-based resin and an acrylic/acrylamide copolymer resin arepreferred.

As the alkali-soluble resin, in particular, a benzyl(meth)acrylate/(meth)acrylic acid copolymer and a multicomponentcopolymer composed of benzyl (meth)acrylate/(meth)acrylic acid/othermonomer are preferred. In addition, a copolymer of 2-hydroxyethylmethacrylate, and a 2-hydroxypropyl (meth)acrylate/polystyrenemacromonomer/benzyl methacrylate/methacrylic acid copolymer, a2-hydroxy-3-phenoxypropyl acrylate/polymethyl methacrylatemacromonomer/benzyl methacrylate/methacrylic acid copolymer, a2-hydroxyethyl methacrylate/polystyrene macromonomer/methylmethacrylate/methacrylic acid copolymer and a 2-hydroxyethylmethacrylate/polystyrene macromonomer/benzyl methacrylate/methacrylicacid copolymer described in JP-A-7-140654 and the like are exemplified.As a commercial product, for example, ACRYLBASE FF-187 and FF-426(produced by Fujikura Kasei Co., Ltd.) are exemplified.

The content of the binder in the curable resin composition is preferablyfrom 1 to 20% by mass, more preferably from 2 to 15% by mass,particularly preferably from 3 to 12% by mass, based on the total solidcontent of the composition.

[5] Filler

The curable resin composition according to the invention may furthercontain a filler. The filler which can be used in the invention includesa spherical silica surface-treated with a silane coupling agent.

The polymerizable composition containing a filler according to theinvention is preferred in view of obtaining an infrared ray cut filterhaving high durability.

The “spherical” as to the spherical filler is sufficient if the particleis not in an acicular, columnar or amorphous shape but is rounded, andthe particle need not be necessarily “perfectly spherical”, but atypical “spherical” shape is a “perfectly spherical” shape.

Whether the filler is spherical can be confirmed by observation througha scanning electron microscope (SEM).

The volume average particle size of the primary particle of the filleris not particularly limited and may be appropriately selected accordingto the purpose, and is preferably from 0.05 to 3 μm, and more preferablyfrom 0.1 to 1 μm. When the volume average particle size of the primaryparticle of the filler is in the range described above, reduction in theprocessability due to development of thixotropic property is suppressedand increase in the maximum particle size is prevented, which isadvantageous in that the generation of defect caused by attachment of aforeign material to the infrared ray cut filter formed or unevenness ofthe coated layer is prevented.

The volume average particle size of the primary particle of the fillercan be measured by a dynamic light scattering particle size distributionmeasuring device.

The filler can be dispersed by using the dispersing agent or binderdescribed above. As described above, the alkali-soluble binder polymerhaving a crosslinkable group in the side chain is particularly preferredfrom the standpoint of curability.

—Surface Treatment—

The surface treatment of the filler is described below. The surfacetreatment of the filler is not particularly limited and may beappropriately selected according to the purpose, and a treatment ofcovering silica with a silane coupling agent is preferred.

—Silane Coupling Agent—

The silane coupling agent used for the surface treatment of the filleris not particularly limited and may be appropriately selected accordingto the purpose, and it preferably has at least one functional groupselected from an alkoxysilyl group, a chlorosilyl group and anacetoxysilyl group (hereinafter, also referred to as a “first functionalgroup”) and at least one functional group selected from a (meth)acryloylgroup, an amino group and an epoxy group (hereinafter, also referred toas a “second functional group”). The second functional group is morepreferably a (meth)acryloyl group or an amino group, and still morepreferably a (meth)acryloyl group. It is advantageous from thestandpoint of preservation stability that the second functional group isa (meth)acryloyl group.

Silane coupling agents containing as the first functional group, atleast one group selected from an alkoxysilyl group, a chlorosilyl groupand an acetoxysilyl group, and as the second functional group, at leastone group selected from an imidazole group, an alkylimidazole group anda vinyl imidazole group described in JP-B-7-68256 can also be preferablyused.

The silane coupling agent is not particularly limited and preferableexamples thereof include γ-aminopropyltriethoxysilane,N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane,N-(β-aminoethyl)-γ-aminopropylmethyldimethoxysilane,γ-glycidoxypropyltrimethoxysilane,γ-glycidoxypropylmethyldimethoxysilane,γ-methacryloxypropyltrimethoxysilane,γ-methacryloxypropylmethyldimethoxysilane, andα[[3-(trimethoxysilyl)propoxy]methyl]imidazole-1-ethanol,2-ethyl-4-methyl-a-[[3-(trimethoxysilyl)propoxy]methyl]imidazole-1-ethanol,4-vinyl-a-[[3-(trimethoxysilyl)propoxy]methyl]imidazole-1-ethanol,2-ethyl-4-methylimidazopropyltrimethoxysilane and salts, intramolecularcondensates and intermolecular condensates thereof described inJP-B-7-68256. The silane coupling agents may be used individually or incombination of two or more thereof.

The surface treatment of the spherical silica with the silane couplingagent may be previously performed only for the spherical silica (in thiscase, hereinafter, the treatment is also referred to as a“pretreatment”) or may be performed together with a part or all of otherfillers contained in the curable resin composition.

The method for performing the pretreatment is not particularly limitedand examples thereof include a dry method, an aqueous solution method,an organic solvent method and a spraying method. The temperature forperforming the pretreatment is not particularly limited and ispreferably from ordinary temperature to 200° C.

At the pretreatment, it is also preferred to add a catalyst. Thecatalyst is not particularly limited and examples thereof include anacid, a base, a metal compound and an organic metal compound.

The amount of the silane coupling agent added when performing thepretreatment is not particularly limited and is preferably from 0.01 to50 parts by mass, more preferably from 0.05 to 50 parts by mass, per 100parts by mass of the spherical silica. When the amount added is in therange described above, the surface treatment sufficient for exhibitingthe effect is performed and reduction in the handling property resultingfrom aggregation of the spherical silica after the treatment issuppressed.

The silane coupling agent has an action of increasing the adhesionproperty between the substrate and the infrared ray cut filter, becausethe first functional group reacts with an active group on the substratesurface, on the spherical silica surface or in the binder, and furtherthe second functional group reacts with a carboxyl group or anethylenically unsaturated group in the binder. On the other hand, thesilane coupling agent has high reactivity and therefore, when the silanecoupling agent itself is added to the polymerizable composition, due toits diffusing action, mainly the second functional group is reacted ordeactivated during preservation to cause a decrease in shelf life or potlife in some cases.

However, when the spherical silica which is pretreated with a silanecoupling agent as described above is used, since the diffusing action issuppressed, the problem in the shelf life or pot life is greatlyimproved and it is possible to make a one-component type composition.Moreover, in the case of applying the pretreatment to the sphericalsilica, since the conditions, for example, stirring condition,temperature condition or use of a catalyst can be feely selected, thereaction rate between the first functional group of the silane couplingagent and the active group of the spherical silica can be significantlyincreased in comparison with the case of adding the spherical silicawithout performing the pretreatment. Therefore, very good results can beobtained particularly in severe characteristics required, for example,electroless gold plating, electroless solder plating and humidityresistance load test. Also, by performing the pretreatment, the amountof the silane coupling agent used can be reduced and the shelf life andpot life can be more improved.

Examples of the spherical silica surface-treated with a silane couplingagent which can be used in the invention include FB and SFP Series ofDenki Kagaku Kogyo Kabushiki Kaisha, 1-FX of Tatsumori Ltd., HSP Seriesof Toagosei Co., Ltd., and SP Series of Fuso Chemical Co., Ltd.

The curable resin composition may or may not contain the filler, and inthe case where the curable resin composition contains the filler,although the content of the filler is not particularly limited and maybe appropriately selected according to the purpose, it is preferablyfrom 1 to 60% by mass based on the total solid content mass of thecurable resin composition. When the content is in the range describedabove, a sufficient reduction in the linear expansion coefficient isachieved and the infrared ray cut filter formed is prevented fromembrittlement and thus, its function as the infrared ray cut filter issufficiently exerted.

[6] Dispersing Agent

In the curable resin composition according to the invention, the dye andthe filler may be dispersed to use by employing a known dispersing agentfor the purpose of enhancing dispersibility and dispersion stabilitythereof.

The dispersing agent which can be used in the invention includes apolymer dispersing agent (for example, polyamidoamine and salt thereof,polycarboxylic acid and salt thereof, a high molecular weightunsaturated acid ester, a modified polyurethane, a modified polyester, amodified poly(meth)acrylate, a (meth)acrylic copolymer or anaphthalenesulfonic acid-formalin condensate), and a surfactant, forexample, a polyoxyethylene alkyl phosphate ester, a polyoxyethylenealkylamine or an alkanolamine.

The polymer dispersing agent can be further classified into astraight-chain polymer, a terminal-modified polymer, a graft polymer anda block polymer according to the structure thereof.

Examples of the terminal-modified polymer having an anchor moiety to thesurface include polymers having a phosphoric acid group at the terminaldescribed, for example, in JP-A-3-112992 and JP-T-2003-533455, polymershaving a sulfonic acid group at the terminal described, for example, inJP-A-2002-273191, polymers having an organic dye partial structure or aheterocyclic ring described, for example, in JP-A-9-77994, and polymersproduced by modifying an oligomer or polymer having a hydroxy group oran amino group at one terminal with an acid anhydride described, forexample, in JP-A-2008-29901. A polymer in which two or more anchormoieties (for example, an acid group, a basic group, an organic dyepartial structure or a heterocyclic ring) to the surface of infrared rayshielding material are introduced into the polymer terminal described inJP-A-2007-277514 is also preferred because of its excellent dispersionstability.

Examples of the graft polymer having an anchor moiety to the surfaceinclude reaction products of a poly(lower alkylene imine) and apolyester described, for example, in JP-A-54-37082, JP-T-8-507960 andJP-A-2009-258668, reaction products of a polyallylamine and a polyesterdescribed, for example, in JP-A-9-169821, amphoteric dispersing resinshaving a basic group and an acidic group described in JP-A-2009-203462,copolymers of a macromonomer and a nitrogen atom-containing monomerdescribed, for example, in JP-A-10-339949 and JP-A-2004-37986, graftpolymers having an organic dye partial structure or a heterocyclic ringdescribed, for example, in JP-A-2003-238837, JP-A-2008-9426 andJP-A-2008-81732, and copolymers of a macromonomer and an acidgroup-containing monomer described, for example, in JP-A-2010-106268.

As to the macromonomer used when producing a graft polymer having ananchor moiety to the surface by radical polymerization, a knownmacromonomer may be used and examples thereof include MACROMONOMER AA-6(polymethyl methacrylate having a terminal group of a methacryloylgroup), AS-6 (polystyrene having a terminal group of a methacryloylgroup), AN-6S (copolymer of an acrylonitrile and a styrene having aterminal group of a methacryloyl group) and AB-6 (polybutyl acrylatehaving a terminal group of a methacryloyl group) produced by ToagoseiCo., Ltd.; PLACCEL FM5 (5 molar equivalent adduct of ε-caprolactone to2-hydroxyethyl methacrylate) and FA10L (10 molar equivalent adduct ofε-caprolactone to 2-hydroxyethyl acrylate) produced by Daicel ChemicalIndustries, Ltd.; and a polyester-based macromonomer described inJP-A-2-272009. Among them, a polyester-based macromonomer excellent inflexibility and solvent affinity is particularly preferred from thestandpoint of dispersibility and dispersion stability of the infraredray shielding material in the composition, and a polyester-basedmacromonomer represented by the polyester-based macromonomer describedin JP-A-2-272009 is most preferred.

As to the block polymer having an anchor moiety to the surface, blockpolymers described, for example, in JP-A-2003-49110 and JP-A-2009-52010are preferred.

The dispersing agent which can be used may be appropriately selected,for example, from known dispersing agents and surfactants.

Specific examples thereof include DISPERBYK 101 (polyamidoaminephosphate), 107 (carboxylic acid ester), 110 (copolymer containing anacid group), 130 (polyamide), 161, 162, 163, 164, 165, 166, 170 (highmolecular weight copolymer) and BYK-P104, P105 (high molecular weightunsaturated polycarboxylic acid) produced by BYK Chemie GmbH; EFKA 4047,4050-4010-4165 (polyurethane-based), EFKA 4330-4340 (block copolymer),4400-4402 (modified polyacrylate), 5010 (polyester amide), 5765 (highmolecular weight polycarboxylate), 6220 (fatty acid polyester) and 6745(phthalocyanine derivative) produced by EFKA; AJISPER PB821, PB822,PB880 and PB881 produced by Ajinomoto Fine Techno Co., Inc.; FLOWLENTG-710 (urethane oligomer) and POLYFLOW No. 50E and No. 300 (acryliccopolymer) produced by Kyoeisha Chemical Co., Ltd.; DISPERON KS-860,873SN, 874, #2150 (aliphatic polyvalent carboxylic acid), #7004(polyetherester), DA-703-50, DA-705 and DA-725 produced by KusumotoChemicals Ltd.; DEMOL RN, N (naphthalenesulfonic acid-formalinpolycondensate), MS, C, SN-B (aromatic sulfonic acid-formalinpolycondensate), HOMOGENOL L-18 (high molecular weight polycarboxylicacid), EMULGEN 920, 930, 935, 985 (polyoxyethylene nonylphenyl ether)and ACETAMIN 86 (stearylamine acetate) produced by Kao Corp.; SOLSPERSE5000 (phthalocyanine derivative), 13240 (polyester amine), 3000, 17000,27000 (polymer having a functional moiety at terminal), 24000, 28000,32000 and 38500 (graft polymer) produce by Lubrizol Japan Ltd.; NIKKOLT106 (polyoxyethylene sorbitan monooleate), MYS-IEX (polyoxyethylenemonostearate) produced by Nikko Chemicals Co., Ltd.; HINOACT T-8000E,produced by Kawaken Fine Chemicals Co., Ltd.; Organosiloxane PolymerKP341, produced by Shin-Etsu Chemical Co., Ltd.; cationic surfactantW001, a nonionic surfactant, for example, polyoxyethylene lauryl ether,polyoxyethylene stearyl ether, polyoxyethylene oleyl ether,polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether,polyethylene glycol dilaurate, polyethylene glycol distearate orsorbitan fatty acid ester and an anionic surfactant, for example, W004,W005 or W017 produced by Yusho Co., Ltd.); EFKA-46, EFKA-47, EFKA-47EA,EFKA Polymer 100, EFKA Polymer 400, EFKA Polymer 401 and EFKA Polymer450 produced by Morishita & Co., Ltd.; a polymer dispersing agent, forexample, DISPERSE AID 6, DISPERSE AID 8, DISPERSE AID 15 and DISPERSEAID 9100 produced by San Nopco Ltd.; ADEKA PLURONIC L31, F38, L42, L44,L61, L64, F68, L72, P95, F77, P84, F87, P94, L101, P103, F108, L121 andP-123 produced by ADEKA Corp.; and IONET (trade name)S-20 produced bySanyo Chemical Industries, Co., Ltd.

The dispersing agents may be used individually or in combination of twoor more thereof. As to the dispersing agent according to the invention,the terminal-modified polymer, graft polymer or block polymer having ananchor moiety to the surface of the infrared ray shielding material mayalso be used in combination with an alkali-soluble resin. Examples ofthe alkali-soluble resin include a (meth)acrylic acid copolymer, anitaconic acid copolymer, a crotonic acid copolymer, a maleic acidcopolymer, a partially esterified maleic acid copolymer, an acidiccellulose derivative having a carboxylic acid in its side chain and aresin obtained by modifying a hydroxy group-containing polymer with anacid anhydride, and particularly a (meth)acrylic acid copolymer ispreferred. Also, N-position substituted maleimide monomer copolymersdescribed in JP-A-10-300922, ether dimer copolymers described inJP-A-2004-300204 and polymerizable group-containing alkali-solubleresins described in JP-A-7-319161 are preferred.

From the standpoint of dispersibility and sedimentation property, resinsdescribed in JP-A-2010-106268 are preferred. In particular, from thestandpoint of dispersibility, a polymer dispersing agent having apolyester chain in its side chain is preferred, and a resin having anacid group and a polyester chain is also preferably exemplified. As tothe acid group in the dispersing agent, in view of adsorptivity, an acidgroup having a pKa of 6 or less is preferred, and particularly acarboxylic acid, a sulfonic acid or a phosphoric acid is preferred.

Specific examples of the resin include specific examples described inparagraphs 0078 to 0111 of JP-A-2010-106268.

In the case where the curable resin composition according to theinvention contains the polymerizable compound and the dispersing agent,it is preferred to prepare first a dispersion composition containing thedye and the dispersing agent by using an appropriate solvent and then toblend the polymerizable composition with the dispersion composition fromthe standpoint of enhancing the dispersibility.

The curable resin composition may or may not contain the dispersingagent, and in the case where curable resin composition contains thedispersing agent, the content of the dispersing agent in the compositionis preferably from 1 to 90% by mass, more preferably from 3 to 70% bymass, based on the mass of the dye contained in the composition.

[7] Sensitizer

The curable resin composition according to the invention may contain asensitizer for the purpose of increasing the radical generatingefficiency of the polymerization initiator and making the photosensitivewavelength longer. The sensitizer which can be used in the invention ispreferably a compound capable of sensitizing the photopolymerizationinitiator described above by an electron transfer mechanism or an energytransfer mechanism. The sensitizer which can be used in the inventionincludes compounds belonging to compound groups described below andhaving an absorption wavelength in the wavelength region from 300 to 450nm.

Preferred examples of the sensitizer include compounds belonging to thefollowing compound groups and having an absorption wavelength in thewavelength region from 330 to 450 nm.

For instance, preferred compounds include a multinuclear aromaticcompound (for example, phenanthrene, anthracene, pyrene, perylene,triphenylene or 9,10-dialkoxyanthracene), a xanthene (for example,fluorescein, eosin, erythrosine, Rhodamine B or rose Bengal), athioxanthone (2,4-diethylthioxanthone, isopropylthioxanthone,diethylthioxanthone or chlorothioxanthone), a cyanine (for example,thiacarbocyanine or oxacarbocyanine), a merocyanine (for example,merocyanine or carbomerocyanine), a phthalocyanine, a thiazine (forexample, thionine, methylene blue or toluidine blue), an acridine (forexample, acridine orange, chloroflavin or acriflavin), an anthraquinone(for example, anthraquinone), a squarylium (for example, squarylium),acridine orange, a coumarin (for example,7-diethylamino-4-methylcoumarin), a ketocoumarin, a phenothiazine, aphenazine, a styrylbenzene, an azo compound, diphenylmethane,triphenylmethane, a distyrylbenzene, a carbazole, porphyrin, a spirocompound, quinacridone, indigo, styryl, a pyrylium compound, apyrromethene compound, a pyrazolotriazole compound, a benzothiazolecompound, a barbituric acid derivative, a thiobarbituric acidderivative, acetophenone, benzophenone, a thioxanthone, an aromaticketone compound, for example, Michler's ketone, and a heterocycliccompound, for example, N-aryloxazolidinone.

Other examples include compounds described in European Patent 568,993,U.S. Pat. Nos. 4,508,811 and 5,227,227, JP-A-2001-125255 andJP-A-11-271969.

The curable resin composition according to the invention may or may notcontain the sensitizer, and in the case where the curable resincomposition contains the sensitizer, the content of the sensitizer ispreferably from 0.01 to 10% by mass, more preferably from 0.1 to 2% bymass, based on the total solid content mass of the curable resincomposition.

[8] Crosslinking Agent

The curable resin composition according to the invention may furthercontain a crosslinking agent for the purpose of increasing the strengthof the dye-containing layer.

As to the crosslinking agent, a compound having a crosslinkable group ispreferred, and a compound having two or more crosslinkable groups ismore preferred. Specific examples of the crosslinkable group preferablyinclude an oxetane group and a cyanate group. Among them, an epoxygroup, an oxetane group and a cyanate group are preferred. Specifically,the crosslinkable agent is particularly preferably an epoxy compound, anoxetane compound or a cyanate compound.

Examples of the epoxy compound which can be preferably used as thecrosslinkable agent in the invention include an epoxy compoundcontaining at least two oxirane groups per molecule and an epoxycompound containing at least two epoxy groups having an alkyl group atthe β-position per molecule.

Examples of the epoxy compound having at least two oxirane groups permolecule include a bixylenol type or biphenol type epoxy compound (forexample, YX4000 produced by Japan Epoxy Resin Co., Ltd.) or a mixturethereof, a heterocyclic epoxy compound having an isocyanurate skeletonor the like (for example, TEPIC produced by Nissan Chemical Industries,Ltd. and ARALDITE PT810 produced by BASF Japan Ltd.), a bisphenol A typeepoxy compound, a novolac type epoxy compound, a bisphenol F type epoxycompound, a hydrogenated bisphenol A type epoxy compound, a bisphenol Stype epoxy compound, a phenol novolac type epoxy compound, a cresolnovolac type epoxy compound, a halogenated epoxy compound (for example,low-brominated epoxy compound, high-halogenated epoxy compound orbrominated phenol novolac type epoxy compound), an allylgroup-containing bisphenol A type epoxy compound, a trisphenolmethanetype epoxy compound, a diphenyldimethanol type epoxy compound, a phenolbiphenylene type epoxy compound, a dicyclopentadiene type epoxy compound(for example, HP-7200 and HP-7200H produced by DIC Corp.), aglycidylamine type epoxy compound (for example, diaminodiphenylmethanetype epoxy compound, glycidylaniline or triglycidylaminophenol), aglycidylester type epoxy compound (for example, diglycidyl phthalate,diglycidyl adipate, diglycidyl hexahydrophthalate or diglycidyldimerate), a hydantoin type epoxy compound, an alicyclic epoxy compound(for example, 3,4-epoxycyclohexylmethyl-3′,4′-epoxycyclohexanecarboxylate, bis(3,4-epoxycyclohexylmethyl)adipate, dicyclopentadienediepoxide or GT-300, GT-400 and ZEHPE 3150 produced by Daicel ChemicalIndustries, Ltd.), an imide type alicyclic epoxy compound, atrihydroxyphenylmethane type epoxy compound, a bisphenol A novolac typeepoxy compound, a tetraphenylolethane type epoxy compound, a glycidylphthalate compound, a tetraglycidyl xylenoylethane compound, anaphthalene group-containing epoxy compound (for example, naphtholaralkyl type epoxy compound, naphthol novolac type epoxy compound ortetrafunctional naphthalene type epoxy compound and as a commercialproduct, ESN-190 and ESN-360 produced by Nippon Steel Chemical Co., Ltd.or HP-4032, EXA-4750 and EXA-4700 produced by DIC Corp.), a reactionproduct of epichlorohydrin and a polyphenol compound which is obtainedby an addition reaction between a phenol compound and a diolefincompound, for example, divinylbenzene and dicyclopentadiene, anepoxidation product of a ring-opening polymerization product of4-vinylcyclohexene-1-oxide compound with peracetic acid or the like, anepoxy compound having a linear phosphorus-containing structure, an epoxycompound having a cyclic phosphorus-containing structure, anα-methylstilbene type liquid crystal epoxy compound, adibenzoyloxybenzene type liquid crystal epoxy compound, an azophenyltype liquid crystal epoxy compound, an azomethine phenyl type liquidcrystal epoxy compound, a binaphthyl type liquid crystal epoxy compound,an azine type epoxy compound, a glycidyl methacrylate copolymer-basedepoxy compound (for example, CP-50S and CP-50M produced by NOF Corp.), acopolymer epoxy compound of cyclohexylmaleimide and glycidylmethacrylate, a bis(glycidyloxyphenyl)fluorene type epoxy compound and abis(glycidyloxyphenyl)adamantane type epoxy compound, but the inventionshould not be construed as being limited thereto. The epoxy resins maybe used individually or in combination of two or more thereof.

Further, other than the epoxy compound containing at least two oxiranegroups per molecule, an epoxy compound containing at least two epoxygroups having an alkyl group at the β-position per molecule can be used.A compound containing an epoxy group substituted with an alkyl group atthe β-position (more specifically, a β-alkyl-substituted glycidyl groupor the like) is particularly preferred.

In the epoxy compounds containing at least an epoxy group having analkyl group at the β-position, all of two or more epoxy groups containedper molecule may be β-alkyl-substituted glycidyl groups or at least oneepoxy group may be a β-alkyl-substituted glycidyl group.

Examples of the oxetane compound include an oxetane resin having atleast two oxetanyl groups per molecule.

Specific examples thereof include a polyfunctional oxetane, for example,bis[(3-methyl-3-oxetanylmethoxy)methyl]ether,bis[(3-ethyl-3-oxetanylmethoxy)methyl]ether,1,4-bis[(3-methyl-3-oxetanylmethoxy)methyl]benzene,1,4-bis[(3-ethyl-3-oxetanylmethoxy)methyl]benzene,(3-methyl-3-oxetanyl)methyl acrylate, (3-ethyl-3-oxetanyl)methylacrylate, (3-methyl-3-oxetanyl)methyl methacrylate,(3-ethyl-3-oxetanyl)methyl methacrylate, or oligomer or copolymerthereof; and an ether compound of a compound having an oxetane group anda compound having a hydroxy group, for example, a novolac resin,poly(p-hydroxystyrene), a cardo-type bisphenol, a calixarene, acalixresorcinarene or silsesquioxane. In addition, a copolymer of anunsaturated monomer having an oxetane ring and an alkyl (meth)acrylateand the like are also exemplified.

Examples of the cyanate compound include a bis A type cyanate compound,a bis F type cyanate compound, a cresol novolac type cyanate compoundand a phenol novolac type cyanate compound.

Also, as the crosslinking agent, melamine or a melamine derivative canbe used.

Examples of the melamine derivative include methylolmelamine and analkylated methylolmelamine (a compound obtained by etherifying amethylol group with methyl, ethyl, butyl or the like).

The crosslinking agents may be used individually or in combination oftwo or more thereof. The crosslinking agent is preferably melamine or analkylated methylolmelamine, particularly preferably a hexamethylatedmethylolmelamine, in view of good preservation stability andeffectiveness in increasing the surface hardness or film strength itselfof the cured film (film after performing a crosslinking reaction due tothe crosslinking agent with energy, for example, light or heat).

The curable resin composition according to the invention may or may notcontain the crosslinking agent, and in the case where the curable resincomposition contains the crosslinking agent, the content of thecrosslinking agent is preferably from 1 to 40% by mass, more preferablyfrom 3 to 20% mass, based on the total solid content mass of the curableresin composition.

[9] Curing Accelerator

The curable resin composition according to the invention may furthercontain a curing accelerator for the purpose of accelerating heat curingof the crosslinking agent, for example, the epoxy compound or oxetanecompound described above.

Examples of the curing accelerator which can be used include an aminecompound (for example, dicyandiamide, benzyldimethylamine,4-(dimethylamino)-N,N-dimethylbenzylamine,4-methoxy-N,N-dimethylbenzylamine or 4-methyl-N,N-dimethylbenzylamine),a quaternary ammonium salt compound (for example, triethylbenzylammoniumchloride), a blocked isocyanate compound (for example, dimethylamine),an imidazole derivative dicyclic amidine compound or salt thereof (forexample, imidazole, 2-methylimidazole, 2-ethylimidazole,2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole,1-cyanoethyl-2-phenylimidazole or1-(2-cyanoethyl)-2-ethyl-4-methylimidazole), a phosphorus compound (forexample, triphenylphosphine), a guanamine compound (for example,melamine, guanamine, acetoguanamine or benzoguanamine), and anS-triazine derivative (for example,2,4-diamino-6-methacryloyloxyethyl-S-triazine,2-vinyl-2,4-diamino-S-triazine,2-vinyl-4,6-diamino-S-triazine-isocyanuric acid adduct or2,4-diamino-6-methacryloyloxyethyl-S-triazine-isocyanuric acid adduct).The curing accelerator is preferably melamine or dicyandiamide.

The curing accelerators may be used individually or in combination oftwo or more thereof.

The curable resin composition according to the invention may or may notcontain the curing accelerator, and in the case where the curable resincomposition contains the curing accelerator, the content of the curingaccelerator is ordinarily from 0.01 to 15% by mass based on the totalsolid content of the curable resin composition.

[10] Elastomer

The curable resin composition according to the invention may furthercontain an elastomer.

By incorporating the elastomer, the adhesion property between thesubstrate and the infrared ray cut filter can be more increased and theheat resistance, heat shock resistance, flexibility and toughness of theinfrared ray cut filter can be more increased.

The elastomer which can be used in the invention is not particularlylimited and may be appropriately selected according to the purpose.Examples thereof include a styrene-based elastomer, an olefin-basedelastomer, a urethane-based elastomer, a polyester-based elastomer, apolyamide-based elastomer, an acrylic-based elastomer and asilicone-based elastomer. The elastomer is composed of a hard segmentcomponent and a soft segment component, wherein ordinarily, the formercontributes to the heat resistance and strength and the lattercontributes to the flexibility and toughness. Of the elastomers, apolyester-based elastomer is advantageous in view of compatibility withother materials.

The styrene-based elastomer specifically includes, for example,TUFPRENE, SOLPRENE T, ASAPRENE T and TUFTEC (produced by Asahi ChemicalIndustry Co., Ltd.), ELASTOMER AR (produced by Aronkasei Co., Ltd.),KRATON G and CALIFLEX (produced by Shell Chemicals Japan Ltd.), JSR-TR,TSR-SIS and DYNARON (produced by JSR Corp.), DENKA STR (produced byDenki Kagaku Kogyo Kabushiki Kaisha), QUINTAC (produced by ZEON Corp.),TPE-SB Series (produced by Sumitomo Chemical Co., Ltd.), RABALON(produced by Mitsubishi Chemical Corp.), SEPTON and HYBRAR (produced byKuraray Co., Ltd.), SUMIFLEX (produced by Sumitomo Bakelite Co., Ltd.),LEOSTOMER and ACTYMER (produced by Riken Vinyl Industry Co., Ltd.).

Specific examples of the olefin-based elastomer include MILASTOMER(produced by Mitsui Petrochemical Industries, Ltd.), EXACT (produced byExxon Chemical Corp.), ENGAGE (produced by Dow Chemical Co.),hydrogenated styrene-butadiene rubber (DYNABON HSBR produced by JSRCorp.), butadiene-acrylonitrile copolymer (NBR Series produced by JSRCorp.), crosslinking point-containing butadiene-acrylonitrile copolymermodified with carboxyl group at both terminals (XER Series produced byJSR Corp.) and epoxidized polybutadiene in which polybutadiene ispartially epoxidized (BF-1000 produced by Nippon Soda Co., Ltd.).

Specific examples of the urethane-based elastomer include PANDEX T-2185and T-2983N (produced by DIC Corp.) and SIRACTRAN E790.

Specific examples of the polyester-based elastomer include HYTREL(produced by Du Pont-Toray Co., Ltd.), PELPRENE (produced by Toyobo Co.,Ltd.) and ESPEL (produced by Hitachi Chemical Co., Ltd.).

The polyamide-based elastomer specifically includes, for example, UBEPolyamide Elastomer (produced by Ube Industries, Ltd.), DAIAMIDE(produced by Daicel-Huels Ltd.), PEBAX (produced by Toray Industries,Inc.), GRILON ELY (EMS-CHEMIE (Japan) Ltd.), NOVAMID (produced byMitsubishi Chemical Corp.) and GRILAX (produced by DIC Corp.).

The acrylic-based elastomer is obtained by copolymerizing an acrylicacid ester, for example, ethyl acrylate, butyl acrylate, methoxyethylacrylate or ethoxyethyl acrylate with an epoxy group-containing monomer,for example, glycidyl methacrylate or allyl glycidyl ether and/or avinyl-based monomer, for example, acrylonitrile or ethylene. Examples ofthe acrylic-based elastomer include an acrylonitrile-butyl acrylatecopolymer, an acrylonitrile-butyl acrylate-ethyl acrylate copolymer andan acrylonitrile-butyl acrylate-glycidyl methacrylate copolymer.

Specific examples of the silicone-based elastomer include KE Series(produced by Shin-Etsu Chemical Co., Ltd.), SE Series, CY Series and SHSeries (produced by Dow Corning Toray Silicone Co., Ltd.).

Other than the elastomers described above, a rubber-modified epoxy resincan be used. The rubber-modified epoxy resin is obtained by modifying apart or all of epoxy groups of, for example, the bisphenol F-type epoxyresin, bisphenol A-type epoxy resin, salicylaldehyde-type epoxy resin,phenol novolac-type epoxy resin or cresol novolac-type epoxy resindescribed above, with both terminal carboxylic acid-modifiedbutadiene-acrylonitrile rubber, terminal amino-modified silicone rubberor the like.

Of the elastomers, from the standpoint of shear adhesion property andheat shock resistance, a both terminal carboxyl group-modifiedbutadiene-acrylonitrile copolymer, a polyester-based elastomer having ahydroxy group (ESPEL 1612 and 1620 produced by Hitachi Chemical Co.,Ltd.) and an epoxidized polybutadiene are preferred.

The curable resin composition according to the invention may or may notcontain the elastomer, and in the case where the curable resincomposition contains the elastomer, although the content of theelastomer is not particularly limited and may be appropriately selectedaccording to the purpose, it is preferably from 0.5 to 30% by mass, morepreferably from 1 to 10% by mass, particularly preferably from 3 to 8%by mass, based on the total solid content mass of the curable resincomposition. It is advantageous that the content is in the preferredrange described above because the shear adhesion property and heat shockresistance can be more improved.

[11] Surfactant

To the curable resin composition according to the invention may be addedvarious surfactants from the standpoint of more improving the coatingproperty. As the surfactant, various surfactants, for example, afluorine-based surfactant, a nonionic surfactant, a cationic surfactant,an anionic surfactant or a silicone-based surfactant may be used.

In particular, by incorporating a fluorine-based surfactant into thecurable resin composition according to the invention, the liquidproperty (particularly, fluidity) of a coating solution prepared fromthe curable resin composition can be more improved so that uniformity ofthe coating thickness and liquid saving property can be more improved.

Specifically, in the case of forming a film using a coating solutionprepared from the curable resin composition containing a fluorine-basedsurfactant, the interfacial tension between a surface to be coated andthe coating solution is reduced, whereby wettability of the surface tobe coated is increased and the coating property onto the surface to becoated is improved. Therefore, even when a thin film of approximatelyseveral μm is formed using a smaller amount of the coating solution, itis effective from the standpoint that a film having a uniform thicknesswith small unevenness in thickness is more preferably formed.

The fluorine content in the fluorine-based surfactant is preferably from3 to 40% by mass, more preferably from 5 to 30% by mass, andparticularly preferably from 7 to 25% by mass. The fluorine-basedsurfactant having the fluorine content of the range described above iseffective in view of the uniformity of the thickness of the coated filmand liquid saving property and also exhibits good solubility in thecurable resin composition.

The fluorine-based surfactant includes, for example, MEGAFAC F171,MEGAFAC F172, MEGAFAC F173, MEGAFAC F176, MEGAFAC F177, MEGAFAC F141,MEGAFAC F142, MEGAFAC F143, MEGAFAC F144, MEGAFAC R30, MEGAFAC F437,MEGAFAC F475, MEGAFAC F479, MEGAFAC F482, MEGAFAC F554, MEGAFAC F780 andMEGAFAC F781 (produced by DIC Corp.), FLUORAD FC430, FLUORAD FC431 andFLUORAD FC171 (produced by Sumitomo 3M Ltd.), and SURFLON S-382, SURFLONSC-101, SURFLON SC-103, SURFLON SC-104, SURFLON SC-105, SURFLON SC-1068,SURFLON SC-381, SURFLON SC-383, SURFLON S-393 and SURFLON KH-40(produced by Asahi Glass Co., Ltd.).

The nonionic surfactant specifically includes, for example,polyoxyethylene lauryl ether, polyoxyethylene stearyl ether,polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether,polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate,polyethylene glycol distearate and a sorbitan fatty acid ester (forexample, PLURONIC L10, L31, L61, L62,10R5, 1782 and 25R2 and TETRONIC304, 701, 704, 901, 904 and 150R1 produced by BASF, and SOLSPERSE 20000produced by Zeneca).

The cationic surfactant specifically includes, for example, aphthalocyanine derivative (trade name: EFKA-745 produced by MorishitaSangyo K.K.), Organosiloxane Polymer KP341 (produced by Shin-EtsuChemical Co., Ltd.), a (meth)acrylic acid (co)polymer (POLYFLOW No. 75,No. 90 and No. 95 (produced by Kyoeisha Chemical Co., Ltd.), and W001(produced by Yusho Co Ltd.).

The anionic surfactant specifically includes, for example, W004, W005and W017 (produced by Yusho Co Ltd.).

The silicone-based surfactant includes, for example, TORAY SILICONEDC3PA, TORAY SILICONE SH7PA, TORAY SILICONE DC11PA, TORAY SILICONESH21PA, TORAY SILICONE SH28PA, TORAY SILICONE SH29PA, TORAY SILICONESH30PA and TORAY SILICONE SH8400 produced by Dow Corning Toray Co.,Ltd., TSF-4440, TSF-4300, TSF-4445, TSF-4460 and TSF-4452 produced byMomentive Performance Materials Inc., KP341, KF6001 and KF6002 producedby Shin-Etsu Silicone Co., Ltd., and BYK-323 and BYK-330 produced byByk-Chemie GmbH.

The surfactants may be used individually or in combination of two ormore thereof.

The curable resin composition according to the invention may or may notcontain the surfactant, and in the case where the curable resincomposition contains the surfactant, the content of the surfactant ispreferably from 0.001 to 1% by mass, more preferably from 0.01 to 0.1%by mass, based on the total solid content mass of the curable resincomposition.

[12] Other Components

In addition to the essential components and preferred additivesdescribed above, other components may be appropriately selected and usedaccording to the purpose in the curable resin composition according tothe invention so long as the effects of the invention are not impaired.

Examples of other components which can be used in combination include aheat curing accelerator, a thermal polymerization inhibitor and aplasticizer. Further, an adhesion accelerator to a surface of thesubstrate, and other auxiliary agents (for example, an electricallyconductive particle, a filler, a defoaming agent, a flame retardant, aleveling agent, a release accelerator, an antioxidant, a perfume, asurface tension-controlling agent or a chain transfer agent) may be usedin combination.

By appropriately incorporating such a component into the curable resincomposition, the properties of the intended infrared ray absorbingfilter, for example, stability or physical property of film can beadjusted.

The thermal polymerization inhibitor is described in detail, forexample, in paragraphs 0101 to 0102 of JP-A-2008-250074.

The plasticizer is described in detail, for example, in paragraphs 0103and 0104 of JP-A-2008-250074.

The adhesion accelerator is described in detail, for example, inparagraphs 0107 to 0109 of JP-A-2008-250074.

Any of the additives described in the patent document above is usable inthe curable resin composition according to the invention.

[13] Solvent

The curable resin composition according to the invention preferablycontains a solvent.

The solvent is not particularly limited, and a solvent capable ofuniformly dissolving or dispersing each component of the curable reincomposition according to the invention may be appropriately selectedaccording to the purpose. Examples of the solvent include an alcohol,for example, methanol, ethanol, normal propanol, isopropanol, normalbutanol, secondary butanol or normal hexanol; a ketone, for example,acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone,diisobutyl ketone, cyclohexanone or cyclopentanone; an ester, forexample, ethyl acetate, butyl acetate, normal amyl acetate, methylsulfate, ethyl propionate, dimethyl phthalate, ethyl benzoate, propyleneglycol monomethyl ether acetate or methoxypropyl acetate; an aromatichydrocarbon, for example, toluene, xylene, benzene or ethylbenzene; ahalogenated hydrocarbon, for example, carbon tetrachloride,trichloroethylene, chloroform, 1,1,1-trichloroethane, methylene chlorideor monochlorobenzene; an ether, for example, tetrahydrofuran, diethylether, ethylene glycol monomethyl ether, ethylene glycol monoethylether, 1-methoxy-2-propanol or propylene glycol monomethyl ether;dimethylformamide, dimethylacetamide, dimethylsulfoxide and sulfolane.The solvents may be used individually or in combination of two or morethereof. Also, a known surfactant may be added.

The curable resin composition according to the invention thus-obtainedhas a solid content concentration preferably from 10 to 90% by mass,more preferably from 15 to 90% by mass, most preferably from 20 to 80%by mass, from the standpoint of being capable of forming adye-containing layer having a film thickness of 20 μm or more which ispreferably applicable to an image sensor chip.

The use of the curable resin composition according to the inventionincludes, for example, use in a dye-containing layer as a near infraredray shielding film on a light-receiving side of a solid-state imagingdevice substrate (for example, for a dye-containing layer as a nearinfrared ray shielding film to a wafer level lens), use in adye-containing layer as a near infrared ray shielding film on a rearside (opposite side to the light-receiving side) of a solid-stateimaging device substrate or use in a dye-containing layer as a nearinfrared ray shielding film in an infrared ray cut filter, and ispreferably use in a dye-containing layer as a near infrared rayshielding film on a light-receiving side of a solid-state imaging devicesubstrate.

The viscosity of the curable resin composition according to theinvention is preferably from 1 mPa·s to 1,000 Pa·s, more preferably from10 mPa·s to 1,000 Pa·s, from the standpoint of thick film-formingproperty capable of forming a dye-containing layer having a filmthickness of 20 μm or more and uniform coating property in the imagesensor chip use. In the case where a coating method is spin coat or slitcoat, the viscosity of the curable resin composition is preferably from1 to 500 mPa·s, more preferably from 10 to 500 mPa·s, and mostpreferably from 20 to 100 mPa·s.

In particular, it is one preferred embodiment that the curable resincomposition according to the invention contains a dye having a maximumabsorption wavelength in a wavelength range from 600 to 850 nm and has asolid content concentration from 10 to 90% by mass and a viscosity at25° C. from 1 mPa·s to 1,000 Pa·s.

In the case where a coating method is screen printing, the viscosity ofthe curable resin composition is preferably from 1 to 1,000 mPa·s, andmost preferably from 5 to 200 mPa·s. Further, in the case of applicatorcoating, the viscosity of the curable resin composition is preferablyfrom 10 mPa·s to 1 Pa·s, and most preferably from 300 to 700 mPa·s.

A formation method of the dye-containing layer includes a method offorming the dye-containing layer by coating the curable resincomposition (coating solution prepared by dissolving, emulsifying ordispersing the solid content of the composition in the solvent describedabove) according to the invention directly on a support, followed bydrying.

The coating method of the curable resin composition (coating solution)on the support is performed by using, for example, an applicator, a spincoater, a slit spin coater, a slit coater or screen printing. Also, itcan be performed by using potting (drop cast method). The applicatorcoating means a coating method wherein after putting a drop of a coatingsolution on a substrate, the coating solution is coated to spread on thesubstrate by a rod-like instrument referred to as an applicator (with agap of several hundred μm between the substrate and the rod).

From the standpoint of forming the dye-containing layer having a filmthickness of 20 μm or more, a recoating wherein after coating, drying,and curing described later, the coating is further repeated plural times(preferably from 2 to 5 times) may be performed.

In particular, in the case of performing the applicator coating, it ispreferred that the solid content concentration and the viscosity of thecurable resin composition according to the invention are from 40 to 70%by mass and from 300 to 700 mPa·s, respectively. Also, the applicatorcoating is preferably performed in a slit width of the applicator from300 to 500 μm and at a moving speed of the applicator from 2 to 5cm/sec.

By using the applicator coating conditions as described above, the filmthickness of the dye-containing layer can be set preferably 50 μm ormore, more preferably from 100 to 300 μm, and still more preferably from200 to 300 μm.

Also, from the standpoint of forming the dye-containing layer having afilm thickness of 20 μm or more, as a method of coating the curableresin composition (coating solution) on the support, a drop cast methodis preferred.

One example of the formation of the dye-containing layer (formation ofthe infrared ray cut filter according to the invention) using the dropcast method is described below.

First, a hydrophilic region is formed on a surface of support, andfurther a hydrophobic region is formed so as to surround the hydrophilicregion. Then, the curable resin composition according to the inventionis drop cast on a surface of the hydrophilic region surrounded with thehydrophobic region. Thus, a uniform film (near infrared ray cut filterusing the curable resin composition according to the invention) can beformed on the surface of the hydrophilic region.

Another example of the formation of the dye-containing layer (formationof the infrared ray cut filter according to the invention) using thedrop cast method is described below.

First, a hydrophilic region is formed on a surface of support, and aresist composition is applied to a surface of the hydrophilic region.Next, the resist composition is subjected to patterning by lithographyto from a resist pattern. As a result, the hydrophilic region surroundedwith the resist pattern (hydrophobic region) is formed. Then, thecurable resin composition according to the invention is applied to thehydrophilic region surrounded with the resist pattern. Subsequently, byremoving the resist pattern a uniform film (near infrared ray cut filterusing the curable resin composition according to the invention) can beformed on the support. By using the region where the resist pattern hasbeen present as a cutting region, the near infrared ray cut filter canbe produced without causing peeling of the near infrared ray cut filter.

It is preferred to have a step of drying the curable resin compositionaccording to the invention applied to the support.

The drying method includes a method of drying by allowing to stand atroom temperature and a method of drying by heating. In the case ofdrying by allowing to stand at room temperature, the drying time is notparticularly limited and, for example, it is preferably 6 hours or more,more preferably 12 hours or more, and still more preferably 18 hours ormore.

The method of drying by heating is not particularly limited. Asdescribed later, in the case where the curable resin compositionaccording to the invention contains water and a polar solvent having aboiling point of 100° C. or higher, a method of continuously heating thecurable resin composition according to the invention applied onto thesupport or a method of heating it in at least two stages of atemperature of 100° C. or less and a temperature exceeding 100° C. ispreferred. In this case, since the water is volatilized first and thepolar solvent having a boiling point of 100° C. or higher is volatilizedlater, when the curable resin composition according to the inventionapplied onto the support is heated, the curable resin compositionaccording to the invention tends to be hard to be dried or curedrapidly. As a result, it is believed that since progress of drying orcuring in the surface vicinity of the film and the inside of the filmcan be uniformed, when a thick film is formed, the surface state defectcan be more effectively inhibited.

In the case of the continuously heating of the curable resin compositionaccording to the invention applied onto the support, it is preferred tocontinuously raise temperature over a temperature from 100° C. or lessto a temperature exceeding 100° C. A temperature range for thecontinuous heating is preferably from 40 to 200° C., more preferablyfrom 50 to 180° C., and still more preferably from 60 to 140° C. Also,the total time for the continuous heating is preferably from 20 to 200minutes, more preferably from 30 to 100 minutes, and still morepreferably from 40 to 80 minutes. It is preferred, for example, to raisetemperature at 1 to 20° C./min.

In the case of the heating in at least two stages of a temperature of100° C. or less and a temperature exceeding 100° C., it is onlynecessary to heat in at least one stage at the temperature of 100° C. orless (preferably 95° C. or less, more preferably 90° C. or less, stillmore preferably 85° C. or less) and the temperature exceeding 100° C.(preferably 105° C. or more, more preferably 110° C. or more, still morepreferably 115° C. or more), respectively, and it is preferred to heatin two or more stages of a temperature of 100° C. or less and atemperature exceeding 100° C., respectively. In the case of the heatingin two stages of a temperature of 100° C. or less and a temperatureexceeding 100° C., a temperature difference in the stages is preferablyfrom 10° C. or more, more preferably 15° C. or more, and still morepreferably 20° C. or more.

It is preferred, for example, to heat in a range from 50 to 70° C., thento heat in a range from 70 to 90° C., then to heat in a range from 90 to110° C., then to heat in a range from 110 to 130° C., and then to heatin a range from 130 to 150° C.

The time for heating at each temperature may be the same or different,and is preferably from 1 to 40 minutes, more preferably from 5 to 30minutes, and still more preferably from 5 to 15 minutes.

The heating device is not particularly limited, can be appropriatelyselected from known devices according to the purpose, and includes, forexample, a dry oven, a hot plate and an IR heater.

Further, the drying conditions of the coated film may be varieddepending on the kinds of each component and solvent, the use ratio andthe like, and are ordinarily at a temperature from 60 to 150° C. forapproximately from 30 seconds to 15 minutes.

The support may be a solid-state imaging device substrate, anothersubstrate (for example, a glass substrate 30 described later) providedon the light-receiving side of the solid-state imaging device substrateor a low refractive index layer or the like provided on thelight-receiving side of the solid-state imaging device substrate.

The film thickness of the dye-containing layer is preferably 20 μm ormore, more preferably from 20 to 300 μm, still more preferably from 20to 200 μm, particularly preferably from 30 to 150 μm, most preferablyfrom 40 to 120 μm, from the standpoint of being capable of preferablyapplying to an image sensor chip. The film thickness is appropriatelyadjusted by the dye used, but by coating in such a thick film thedesired infrared ray cut function can be achieved without limitation ofthe kind of dye used.

Further, the dye-containing layer may be composed of multiple layers.For example, a copper complex is incorporated into a firstdye-containing layer (copper complex-containing layer) and a dyedifferent from the copper complex (preferably a pyrrolopyrrole dye) isincorporated into a second dye-containing layer. The film thickness ofthe copper complex-containing layer is preferably composed of the thicklayer described above, and specifically 50 μm or more. The filmthickness of the second dye-containing layer is preferably 10 μm orless, more preferably 5 μm or less, and particularly preferably 3 μm orless. By using two different kinds of dyes in combination, light havingthe desired wavelength can be shielded, and by covering the seconddye-containing layer with the copper complex-containing layer, even whenthe heat resistance of the dye in the second dye-containing layer isinsufficient, it can endure the reflow process.

The method of forming the dye-containing layer using the curable resincomposition according to the invention may contain other steps.

The other steps are not particularly limited, can be appropriatelyselected according to the purpose, and include, for example, a surfacetreatment step of substrate, a pre-heating step (prebake step), a curingtreatment step and a post-heating step (postbake step).

<Pre-Heating Step and Post-Heating Step>

The heating temperature in the pre-heating step and post-heating step isordinarily from 80 to 200° C., and preferably from 90 to 150° C.

The heating time in the pre-heating step and post-heating step isordinarily from 30 to 240 seconds, and preferably from 60 to 180seconds.

<Curing Treatment Step>

The curing treatment step is a step of applying a curing treatment tothe film formed, if desired. By conducting the treatment, the mechanicalstrength of the dye-containing layer is enhanced.

The curing treatment step is not particularly limited, can beappropriately selected according to the purpose, and preferablyincludes, for example, an entire surface exposure treatment and anentire surface heating treatment. The term “exposure” as used in theinvention means and includes not only exposure to light having variouswavelengths but also irradiation with radiation, for example, anelectron beam or an X-ray.

The exposure is preferably performed by the irradiation with radiationand as the radiation usable at the exposure, in particular, an electronbeam, KrF, ArF, an ultraviolet light, for example, g-line, h-line ori-line, or visible light is preferably used. KrF, g-line, h-line ori-line is preferred.

Examples of the exposure system include stepper exposure and exposurewith a high-pressure mercury lamp.

The exposure amount is preferably from 5 to 3,000 mJ/cm², morepreferably from 10 to 2,000 mJ/cm², and most preferably from 50 to 1,000mJ/cm².

Examples of the method for the entire surface exposure treatment includea method of exposing the entire surface of the film formed. By theentire surface exposure, in the case where the curable resin compositioncontains a polymerizable compound, curing of the polymerizationcomponent in the film formed from the curable resin composition isaccelerated and curing of the film formed is further proceeds, therebyimproving the mechanical strength and durability.

The apparatus for conducting the entire surface exposure is notparticularly limited, can be appropriately selected according to thepurpose, and preferably includes an UV exposure machine, for example, anultrahigh-pressure mercury lamp.

Also, the method for the entire surface heating treatment includes amethod of heating the entire surface of the film formed. BY the entiresurface heating, the film strength of the pattern is enhanced.

The heating temperature at the entire surface heating is preferably from120 to 250° C., and more preferably from 120 to 250° C. When the heatingtemperature is 120° C. or more, the film strength is increased by theheat treatment, and when the heating temperature is 250° C. or less, theoccurrence of decomposition of the components in the film to weaken andembrittle the film quality can be prevented.

The heating time in the entire surface heating is preferably from 3 to180 minutes, and more preferably from 5 to 120 minutes.

The apparatus for conducting the entire surface heating is notparticularly limited, can be appropriately selected from knownapparatuses according to the purpose, and includes, for example, a dryoven, a hot plate and an IR heater.

The dye-containing layer obtained by using the curable resin compositionaccording to the invention described above has a high light-shieldingproperty in the near infrared region around wavelength of 700 nm (nearinfrared ray shielding property) and a high light-transmitting propertyin the visible region (visible light transmitting property) because itis formed from the curable resin composition according to the invention.

<Camera Module>

The invention also relates to a camera module comprising a solid-stateimaging device substrate and the dye-containing layer provided on alight-receiving side of the solid-state imaging device substrate.

The camera module according to one preferred embodiment of the inventionis described below with reference to FIG. 1 and FIG. 2, but theinvention should not be construed as being limited thereto.

The portions common between FIG. 1 and FIG. 2 are indicated by a commonreference numeral or sign.

Also, in the description, the terms “top”, “above” and “upper side” eachindicates a side farther from a silicon substrate 10, and the terms“bottom”, “below” and “lower side” each indicates a side closer to thesilicon substrate 10.

FIG. 1 is a schematic cross-sectional view showing a configuration of acamera module equipped with an image sensor chip.

The camera module 200 shown in FIG. 1 is connected to a circuit board 70as a mounting substrate through a solder ball 60 as a connection member.

More specifically, the camera module 200 is configured to comprise asolid-state imaging device substrate 100 having an image-forming deviceunit on a first major surface of a silicon substrate, a dye-containinglayer 42 provided on the solid-state imaging device substrate 100, aglass substrate 30 (light-transmitting substrate) disposed above thedye-containing layer 42, an infrared ray reflecting film 35 disposedabove the glass substrate 30, a lens holder 50 having an imaging lens 40in an internal space and being disposed above the glass substrate 30,and a light-shielding and electromagnetic shield 44 disposed so as tosurround the periphery of the solid-state imaging device substrate 100and the glass substrate 30. Respective members are adhered usingadhesives 20 (not shown in FIGS. 1) and 45.

In the camera module 200, incident light hv from the outsidesequentially passes through the imaging lens 40, the infrared rayreflecting film 35, the glass substrate 30 and the dye-containing layer42 so as to reach the imaging device unit of the solid-state imagingdevice substrate 100.

Also, the camera module 200 is connected to a circuit board 70 throughthe solder ball 60 (connection material) on the second major surfaceside of the solid-state imaging device substrate 100.

FIG. 2 is an enlarged cross-sectional view of the solid-state imagingdevice substrate 100 in FIG. 1.

The solid-state imaging device substrate 100 is configured to comprise asilicon substrate 10 as a base material, an imaging device 12, aninterlayer insulating film 13, a base layer 14, a red color filter 15R,a green color filter 15G, a blue color filter 15B, an overcoat 16, ahigh refractive index layer (microlens) 17, a low refractive indexlayer, a light-shielding film 18, an insulating film 22, a metalelectrode 23, a solder resist layer 24, an internal electrode 26 and adevice surface electrode 27.

However, the solder resist layer 24 may be omitted.

First, the configuration on the first major surface side(light-receiving side) of the solid-state imaging device substrate 100is mainly described below.

As shown in FIG. 2, an imaging device unit where a plurality of imagingdevices 12, for example, CCD and CMOS are two-dimensionally arrayed isprovided on the first major surface side of the silicon substrate 10which is the base material of the solid-state imaging device substrate100.

The interlayer insulating film 13 is formed on the imaging device 12 inthe imaging device unit, and the base layer 14 is formed on theinterlayer insulating film 13. Further, the red color filter 15R, thegreen color filter 15G and the blue color filter 15B (hereinafter, theseare collectively referred to as a “color filter 15” sometimes)corresponding to respective imaging devices 12 are disposed on the baselayer 14, respectively.

A light-shielding film not shown may be provided in the boundaries ofthe red color filter 15R, the green color filter 15G and the blue colorfilter 15B and in the periphery of the imaging device unit. Thelight-shielding film can be produced, for example, using a known blackcolor resist.

The overcoat 16 is formed on the color filter 15, and the highrefractive index layer 17 is formed on the overcoat 16 so as tocorrespond to the imaging device 12 (color filter 15).

Further, the low refractive index layer 46 is provided on the highrefractive index layer 17.

Also, in the periphery of the imaging device unit on the first majorsurface side, a peripheral circuit (not shown) and the internalelectrode 26 are provided, and the internal electrode 26 is electricallyconnected to the imaging device 12 through the peripheral circuit.

Further, the device surface electrode 27 is formed on the internalelectrode 26 through the interlayer insulating film 13. In theinterlayer insulating film 13 between the internal electrode 26 and thedevice surface electrode 27, a contact plug (not shown) for electricallyconnecting these electrodes is formed. The device surface electrode 27is used for voltage application, signal reading and the like though thecontact plug and the internal electrode 26.

The base layer 14 is formed on the device surface electrode 27. Theovercoat 16 is formed on the base layer 14. The base layer 14 and theovercoat 16 formed on the device surface electrode 27 are opened to forma pad opening and to expose a part of the device surface electrode 27.

On the first major surface side of the solid-state imaging devicesubstrate 100, the adhesive 20 is provided in the periphery of theimaging device unit, and the solid-state imaging device substrate 100and the glass substrate 30 are adhered through the adhesive 20.

The silicon substrate 10 has a through-hole penetrating the siliconsubstrate 10, and a penetrating electrode which is a part of the metalelectrode 23 is provided in the through-hole. The imaging device unitand the circuit board 70 are electrically connected by the penetratingelectrode.

Next, the configuration on the second major surface side of thesolid-state imaging device substrate 100 is mainly described below.

On the second major surface side, the insulating film 22 is formed fromthe second major surface to the inner wall of the through-hole.

On the insulating film 22, the metal electrode 23 patterned to extendfrom the region on the second major surface of the silicon substrate 10to the inside of the through hole is provided. The metal electrode 23 isan electrode for connecting the imaging device unit in the solid-stateimaging device substrate 100 and the circuit board 70.

The penetrating electrode is the portion formed inside the through holeof the metal electrode 23. The penetrating electrode penetrates thesilicon substrate 10 and a part of the interlayer insulating film andreaches the lower side of the internal electrode 26 to be electricallyconnected to the internal electrode 26.

Further, on the second major surface side, the solder resist layer 24(protective insulating film) covering the second major surface on whichthe metal electrode 23 is formed and having an opening to expose a partof the metal electrode 23 is provided.

Further, on the second major surface side, the light-shielding film 18covering the second major surface on which the solder resist layer 24 isformed and having an opening to expose a part of the metal electrode 23is provided.

In FIG. 2, although the light-shielding film 18 is patterned so as tocover a part of the metal electrode 23 and to expose the remainingportion, it may be patterned to expose the entirety of the metalelectrode 23 (the same applies to the patterning of the solder resistlayer 24).

Also, the solder resist layer 24 may be omitted and the light-shieldingfilm 18 may be formed directly on the second major surface where themetal electrode 23 is formed.

The solder ball 60 as a connection member is provided on the exposedmetal electrode 23, and the metal electrode 23 of the solid-stateimaging device substrate 100 and a connection electrode not shown of thecircuit board 70 are electrically connected through the solder ball 60.

The configuration of the solid-state imaging device substrate 100 hasbeen described above, and the solid-state imaging device substrate 100can be formed by a known method, for example, a method described inparagraphs 0033 to 0068 of JP-A-2009-158863 or a method described inparagraphs 0036 to 0065 of JP-A-2009-99591.

The interlayer insulating film 13 is formed, for example, by sputteringor CVD (chemical vapor deposition) as an SiO₂ film or an SiN film.

The color filter 15 is formed by photolithography, for example, using aknown color resist.

The overcoat 16 and the base layer 14 are formed by photolithographyusing, for example, a known resist for forming an organic interlayerfilm.

The microlens 17 is formed, for example, by photolithography using astyrene-based resin or the like.

The solder resist layer 24 is preferably formed by photolithographyusing a known solder resist containing, for example, a phenolic resin, apolyimide-based resin or an amine-based resin.

The solder ball 60 is formed as a sphere having, for example, a diameterfrom 100 to 1,000 μm (preferably a diameter from 150 to 700 μm).

The internal electrode 26 and the device surface electrode 27 areformed, for example, by CMP (chemical mechanical polishing) orphotolithography and etching, as a metal electrode, for example, of Cu.

The metal electrode 23 is formed as a metal electrode, for example, ofCu, Au, Al, Ni, W, Pt, Mo, a Cu compound, a W compound or a Mo compound.The metal electrode 23 may have a sing-layer configuration or amultilayer configuration composed of two or more layers. The filmthickness of the metal electrode 23 is, for example, from 0.1 to 20 μm(preferably from 0.1 to 10 μm). The silicon substrate 10 is notparticularly limited, and a silicon substrate thinned by grinding theback surface of the substrate may be used. The thickness of thesubstrate is not limited and, for example, a silicon wafer having athickness from 20 to 200 μm (preferably from 30 to 150 μm) is used.

The through-hole of the silicon substrate 10 is formed, for example, byphotolithography or RIE (reactive ion etching).

One embodiment of the camera module has been described hereinbefore withreference to FIG. 1 and FIG. 2, but the embodiment above is not limitedto the configuration of FIG. 1 and FIG. 2.

Also, the invention relates to an infrared ray cut filter comprising thedye-containing layer described above, as an infrared ray shielding film,provided on a light-transmitting substrate, for example, a glasssubstrate.

The infrared ray cut filter according to the invention may be aninfrared ray cut filter comprising two or more dye-containing layers, asa near infrared ray shielding film, provided on a light-transmittingsubstrate.

For example, an infrared ray cut filter comprising a firstdye-containing layer containing a copper complex and a seconddye-containing layer containing a pyrrolopyrrole dye is preferred fromthe standpoint of the heat resistance in the reflow process.

The infrared ray cut filter comprising two or more dye-containing layerscan be formed by coating, drying, and curing described later using acurable resin composition containing a dye having a maximum absorptionwavelength in a wavelength range from 600 to 850 nm to from adye-containing layer, and then using a curable resin compositioncontaining a dye which is different from the dye described above and mayhave a maximum absorption wavelength in a wavelength range from 600 to850 nm.

The infrared ray cut filter according to the invention can be subjectedto a solder reflow process. The production of camera module by thesolder reflow process makes automatic mounting of electronic componentmounting substrate and the like requiring to perform soldering possible,and productivity can be significantly improved in comparison with thecase where the solder reflow process is not used. Further, since themounting can be performed automatically, it is possible to reduce thecost. In the case where the infrared ray cut filter is subjected to thesolder reflow process, since the infrared ray cut filter is exposed to atemperature approximately from 250 to 270° C., it is preferred for theinfrared ray cut filter to have heat resistance endurable the solderreflow process (hereinafter, also referred to as “solder reflowresistance”).

In the specification, the phrase “having a solder reflow resistance”means that the property of the infrared ray cut filter is maintainedbefore and after performing the heating at 250° C. for 10 minutes. Morepreferably, the property is maintained before and after performing theheating at 260° C. for 10 minutes. Still more preferably, the propertyis maintained before and after performing the heating at 270° C. for 3minutes. In the case of having no solder reflow resistance, when theinfrared ray cut filter is maintained under the conditions describedabove, the infrared ray absorbing ability of the infrared ray cut filterdeteriorates and the function as a film becomes insufficient in somecases.

Further, the invention relates to a production method of camera moduleincluding a step of the reflow processing.

The infrared ray cut filter according to the invention can maintain theinfrared ray absorbing ability even when it is subjected to the solderreflow process so that the characteristics of compact, lightweight andhigh-performance camera module are not destroyed.

As described above, in the case of performing the solder reflow process,since a reflow furnace is heated with hot air, a far infrared ray or thelike, the infrared ray cut filter is required to have heat resistancecapable of responding to the reflow temperature.

<Image Sensor Chip and Production Method Thereof>

The invention also relates to an image sensor chip which can bepreferably used for the camera module described above and a productionmethod thereof.

FIG. 3A and FIG. 3B are both schematic cross-sectional views showing anembodiment of the production method of image sensor chip according tothe invention.

As shown in FIG. 3A and FIG. 3B, the production method of image sensorchip according to the invention comprises a step of coating the curableresin composition described above on a glass substrate 30 to form adye-containing layer 42, and a step of adhering the glass substrate 30having the dye-containing layer 42 formed onto a solid-state imagingdevice substrate 100 (in FIGS. 3A and 3B, a low refractive index layer46 of the substrate).

As shown in FIG. 3A and FIG. 3B, it is preferred that the glasssubstrate 30 further has an infrared ray reflecting film 35.

According to the production method of image sensor chip of theinvention, an image sensor chip comprising a solid-state imaging devicesubstrate 100 (in FIGS. 3A and 3B, a low refractive index layer 46 ofthe substrate), a dye-containing layer 42 and a glass substrate 30having an infrared ray reflecting film 35, wherein these members areclosely contacted with each other without intervention of an air layercan be produced.

In the production method of image sensor chip according to theinvention, a surface of the glass substrate 30 on which the infrared rayreflecting film 35 is not formed (surface on which the dye-containinglayer 42 is formed) may be adhered to the solid-state imaging devicesubstrate 100 as the embodiment shown in FIG. 3A or a surface of theglass substrate 30 on which the infrared ray reflecting film 35 isformed may be adhered to the solid-state imaging device substrate 100 asthe embodiment shown in FIG. 3B.

According to the embodiment of the production method of image sensorchip of the invention shown in FIG. 3A, an image sensor chip having theinfrared ray reflecting film 35 on a surface of the glass substrate 30opposite to the dye-containing layer 42 can be produced.

According to the embodiment of the production method of image sensorchip of the invention shown in FIG. 3B, an image sensor chip having theinfrared ray reflecting film 35 between the dye-containing layer 42 andthe solid-state imaging device substrate 100 (in FIGS. 3A and 3B, a lowrefractive index layer 46 of the substrate) can be produced.

According to the invention, a stack containing a dye-containing layer 42as a near infrared ray shielding film, a glass substrate 30 and aninfrared ray reflecting film 35 is able to function as an infrared raycut filter.

In the invention, the infrared ray reflecting film 35 is notparticularly limited, and is preferably a dielectric multilayer film.The dielectric multilayer film for use in the invention is a film havinga function of reflecting and/or absorbing a near infrared ray.

According to the invention, on a solid-state imaging device substrate100 (in FIGS. 3A and 3B, a low refractive index layer 46 of thesubstrate), a stack in which a dye-containing layer 42 formed from thecurable resin composition described above, a glass substrate 30 and adielectric multilayer film as an infrared ray reflecting film 35 arecontinuously provided in this order may be formed as the embodimentshown in FIG. 3A, or a stack in which a dielectric multilayer film as aninfrared ray reflecting film 35, a dye-containing layer 42 and a glasssubstrate 30 are continuously provided in this order may be formed asthe embodiment shown in FIG. 3B.

As a material of the dielectric multilayer film, for example, ceramiccan be used. In order to form a near infrared ray cut filter utilizingthe interference effect of light, it is preferred to use two or moreceramics having different refractive indexes.

Alternatively, it is also preferred to use a noble metal film having anabsorption in the hear infrared region by considering the thickness andthe number of layers so as not to affect the transmittance of visiblelight of the near infrared ray cut filter.

As the dielectric multilayer film, specifically, a structure in which ahigh refractive index material and a low refractive index material arealternatively stacked can be preferably used.

As a material constituting the high refractive index material layer, amaterial having a refractive index of 1.7 or more can be used, and amaterial having a refractive index ranging from 1.7 to 2.5 is ordinarilyselected.

As the material, for example, titanium oxide (titania), zirconium oxide,tantalum pentoxide, niobium pentoxide, lanthanum oxide, yttrium oxide,zinc oxide, zinc sulfide, indium oxide, and materials containing theseoxides as the main component and a small amount of titanium oxide, tinoxide and/or cerium oxide are exemplified. Among them, titanium oxide(titania) is preferred.

As a material constituting the low refractive index material layer, amaterial having a refractive index of 1.6 or less can be used, and amaterial having a refractive index ranging from 1.2 to 1.6 is ordinarilyselected.

As the material, for example, silica, alumina, lanthanum fluoride,magnesium fluoride and sodium aluminum hexafluoride are exemplified.Among them, silica is preferred.

The thickness of each of the high refractive index material layer andthe low refractive index material layer is ordinarily a value from 0.1to 0.5λ, wherein X (nm) is a wavelength of infrared ray to be shielded.When the thickness is out of the range described above, the product (n xd) of the refractive index (n) and the film thickness (d) is widelydifferent from the optical film thickness calculated from 214 and therelationship between the optical properties of reflection and refractioncollapses so that the blocking and transmission of a specific wavelengthtends to be difficult to control.

Further, the number of layers in the dielectric multilayer film ispreferably from 5 to 50 layers, and more preferably from 10 to 45layers.

The formation method of the dielectric multilayer film is notparticularly limited, and includes, for example, a method wherein a highrefractive index material and a low refractive index material arealternatively stacked, for example, by a CVD method, a sputtering methodor a vacuum deposition method to form a dielectric multilayer film andthe dielectric multilayer film is adhered to the film described abovewith an adhesive or a method wherein a high refractive index materialand a low refractive index material are alternatively stacked directlyon the film described above, for example, by a CVD method, a sputteringmethod or a vacuum deposition method to form to form a dielectricmultilayer film.

Further, in the case where a warp occurs in the substrate when adielectric multilayer film is deposited, in order to solve the problem,a method may be taken, for example, of depositing the dielectricmultilayer film onto the both surface of the substrate or of irradiatingradiation, for example, an ultraviolet ray on the surface of thesubstrate on which the dielectric multilayer film is deposited. In thecase of irradiating radiation, the irradiation may be performed whileconducting the deposition of dielectric multilayer film, or may beseparately performed after the deposition.

In the production method of image sensor chip according to theinvention, the glass substrate 30 further has an antireflection film(not shown in FIGS. 3A and 3B).

For example, the infrared ray reflecting film 35 may be formed on onesurface of the glass substrate 30 and the antireflection film may beformed on the other surface of the glass substrate 30.

By the further formation of the antireflection film on the glasssubstrate 30, the antireflection film is further provided on theoutermost surface of the image sensor chip comprising the solid-stateimaging device substrate 100, the dye-containing layer 42 and the glasssubstrate 30 having the infrared ray reflecting film 35.

The antireflection film for use in the invention is not particularlylimited so long as it can prevent or reduce the reflection of visiblelight.

The antireflection film can be formed, for example, by stacking from 1to 5 layers of the high refractive index material and the low refractiveindex material described as to the dielectric multilayer film using, forexample, a CVD method, a sputtering method or a vacuum depositionmethod. In addition, a method wherein a heat and/or UV curable materialis coated on a surface of glass substrate 30, fine shape, for example,conical shape having from several tens to several hundred nm order istransferred onto the material using a mold or the like, and the materialis cured with heat and/or UV to form an antireflection film, or a method(wet coating) wherein sol-gel materials having different refractiveindexes (material containing a colloidal substance obtained byhydrolysis and polymerization of an alkoxide or the like dispersed in asolution) are coated to stack, thereby forming an antireflection filmcan be used. In the case of using the sol-gel material, curing isordinarily performed using heat, but the antireflection film may beformed by using an energy ray (for example, an ultraviolet ray) togenerate an acid or the like, which is a condensation catalyst, therebyperforming curing, that is, so-called photocuring (JP-A-2000-109560 andJP-A-2000-1648).

Among them, from the standpoint that the material and equipment used inthe formation of dielectric multilayer film are used as they are, amethod of forming the antireflection film in the same manner as in theformation of dielectric multilayer film, or from the standpoint ofincrease in productivity, a method of forming the antireflection film bythe wet coating described above can be preferably used.

The thickness of the antireflection film is not particularly limited solong as the effect of the invention is not damaged, and it is preferablyfrom 0.01 to 1.0 μm, and more preferably from 0.05 to 0.5 μm.

Further, as the infrared ray reflecting film 35 and the antireflectionfilm, the dielectric multilayer film and the antireflection film used inthe examples described in paragraph 0083 or later of JP-A-2013-68688 canalso be used.

EXAMPLE

Examples of the invention will be described below, but the inventionshould not be construed as being limited thereto. All “part” and “%”therein are mass basis unless otherwise specified.

Also, the measurement of viscosity in the examples below was conductedusing a viscosity measuring device (RE85L Model Viscometer produced byTold Sangyo Co., Ltd.) under the conditions described below.

Rotor: Standard cone rotor for RE85L Model Viscometer 1° 34′×R24Rotation number: setting appropriately in a range from 0.5 to 100 rpmdepending on viscosity of thematerial to be measuredMeasurement temperature: 25° C.

<Preparation of Curable Resin Composition> Example 1

The composition components described below were mixed by a mixer toprepare a curable resin composition of Example 1.

Phthalocyanine-based dye A (EXCOLOR TX-EX 0.5 parts by mass 720 producedby Nippon Shokubai Co., Ltd.; maximum absorption wavelength (λ_(max)) =720 nm (film)) Polymerizable compound 1 shown below 25 parts by massPolymerizable compound 2 shown below 25 parts by mass Propylene glycolmonomethyl ether acetate 49.5 parts by mass (PEGMEA)

Polymerizable Compound 1

Polymerizable Compound 2

Example 2

A curable resin composition of Example 2 was prepared in the same manneras in Example 1 except that 0.25 parts by mass of Phthalocyanine-baseddye A described and 0.25 parts by mass of Phthalocyanine-based dye B(EXCOLOR TX-EX 708K produced by Nippon Shokubai Co., Ltd.; maximumabsorption wavelength (λ_(max))=755 nm (film)) were used in place of 0.5parts by mass of Phthalocyanine-based dye A.

Example 3

A curable resin composition of Example 3 was prepared in the same manneras in Example 1 except that 0.25 parts by mass of Phthalocyanine-baseddye A described above and 0.25 parts by mass of a cyanine-based dye(Daito Chmix 1371F produced by Daito Chemix Corp.; maximum absorptionwavelength (λ_(max))=805 nm (film)) were used in place of 0.5 parts bymass of Phthalocyanine-based dye A.

Example 4

A curable resin composition of Example 4 was prepared in the same manneras in Example 1 except that 0.25 parts by mass of Phthalocyanine-baseddye A described above and 0.05 parts by mass of a quatenylene-based dye(Lumogen IR765 produced by BASF; maximum absorption wavelength(λ_(max))=705 nm (film)) were used in place of 0.5 parts by mass ofPhthalocyanine-based dye A.

Example 5

A curable resin composition of Example 5 was prepared in the same manneras in Example 1 except that 0.5 parts by mass of Phthalocyanine-baseddye B (EXCOLOR TX-EX 708K produced by Nippon Shokubai Co., Ltd.; maximumabsorption wavelength (λ_(max))=755 nm (film)) was used in place of 0.5parts by mass of Phthalocyanine-based dye A.

Example 6

A curable resin composition of Example 6 was prepared in the same manneras in Example 1 except that 0.25 parts by mass of Phthalocyanine-baseddye B (EXCOLOR TX-EX 708K produced by Nippon Shokubai Co., Ltd.; maximumabsorption wavelength (λ_(max))=755 nm (film)) and 0.25 parts by mass ofa cyanine-based dye (Daito Chmix 1371F produced by Daito Chemix Corp.;maximum absorption wavelength (λ_(max))=805 nm (film)) were used inplace of 0.5 parts by mass of Phthalocyanine-based dye A.

Example 7

A curable resin composition of Example 7 was prepared in the same manneras in Example 1 except that 0.25 parts by mass of Phthalocyanine-baseddye B (EXCOLOR TX-EX 708K produced by Nippon Shokubai Co., Ltd.; maximumabsorption wavelength (λ_(max))=755 nm (film)) and 0.25 parts by mass ofa quaterrylene-based dye (Lumogen IR765 produced by BASF; maximumabsorption wavelength (λ_(max))=705 nm (film)) were used in place of 0.5parts by mass of Phthalocyanine-based dye A.

Example 8

A curable resin composition of Example 8 was prepared in the same manneras in Example 1 except that 0.5 parts by mass of a cyanine-based dye(Daito Chmix 1371F produced by Daito Chemix Corp.; maximum absorptionwavelength (λ_(max))=805 nm (film)) was used in place of 0.5 parts bymass of Phthalocyanine-based dye A.

Example 9

A curable resin composition of Example 9 was prepared in the same manneras in Example 1 except that 0.25 parts by mass of a cyanine-based dye(Daito Chmix 1371F produced by Daito Chemix Corp.; maximum absorptionwavelength (λ_(max))=805 nm (film)) and 0.25 parts by mass of aquaterrylene-based dye (Lumogen IR765 produced by BASF; maximumabsorption wavelength (λ_(max))=705 nm (film)) were used in place of 0.5parts by mass of Phthalocyanine-based dye A.

Example 10

A curable resin composition of Example 10 was prepared in the samemanner as in Example 1 except that 0.5 parts by mass of aquaterrylene-based dye (Lumogen IR765 produced by BASF; maximumabsorption wavelength (λ_(max))=705 nm (film)) was used in place of 0.5parts by mass of Phthalocyanine-based dye A.

Example 11

A curable resin composition of Example 11 was prepared in the samemanner as in Example 1 except that 25 parts by mass of ARONIX M-305(produced by Toagosei Co., Ltd.) was used in place of 25 parts by massof Polymerizable compound 1.

Example 12

A curable resin composition of Example 12 was prepared in the samemanner as in Example 1 except that 25 parts by mass of CYCLOMER P ACA230AA (produced by Daicel Chemical Industries, Ltd.) was used in placeof 25 parts by mass of Polymerizable compound 2.

Example 13

A curable resin composition of Example 13 was prepared in the samemanner as in Example 1 except that 25 parts by mass of ARONIX M-305(produced by Toagosei Co., Ltd.) and 25 parts by weight of CYCLOMER PACA 230AA (produced by Daicel Chemical Industries, Ltd.) were used inplace of 25 parts by mass of Polymerizable compound 1 and 25 parts bymass of Polymerizable compound 2, respectively.

Example 14

A curable resin composition of Example 14 was prepared in the samemanner as in Example 1 except that 49.5 parts by mass of propyleneglycol monomethyl ether (PGME) was used in place of 49.5 parts by massof PGMEA.

<Production of Image Sensor Chip>

First, a wafer having formed thereon CMOS sensor equipped with aplurality of light-receiving elements composed of photodiode(light-receiving unit size 1.0 μm×1.0 μm) having a pixel light-receivingunit pitch of 2.0 μm and 2592 pixels (X axis direction)×1944 pixels (Yaxis direction) arranged two-dimensionally at a certain arrangementpitch on a substrate, an insulating layer (silicon oxide) having awiring layer composed of A1 and a light-shielding layer, a passivationlayer (silicon nitride), and a waveguide (silicon nitride) was prepared.In the COMS sensor, the thickness of the passivation layer was set to0.3 μm, the thickness of the insulating layer intervening between thepassivation layer and the waveguide was set to 0.3 μm, and the thicknessof the waveguide was set to 2.1 μm. The entrance plane dimension of thewaveguide was set to 1.5 μm×1.5 μm, and the exit plane dimension of thewaveguide was set to 1.0 μm×1.0 μm same as the dimension of thephotodiode. As a result of measuring the refractive indexes of thepassivation layer, the insulating layer and the waveguide by a spectralellipsometer, the refractive index of the passivation layer was 2.0, therefractive index of the insulating layer was 1.46, the refractive indexof the waveguide was 1.88, and the refractive index of the insulatinglayer outside of the waveguide was 1.46. The value of the refractiveindex, including henceforth, is a value at a wavelength of 550 nm,unless particularly specified in the wavelength.

(Formation of Lower Planarizing Layer)

A photocurable type acrylic transparent resin material (CT-2020Lproduced by Fujifilm Electronic Materials Co., Ltd.) was spincoated onthe passivation layer, followed by performing prebake, ultraviolet rayentire surface exposure and postbake to form a lower planarizing layer(thickness: 0.3 μm). As a result of measuring the refractive index ofthe lower planarizing layer in the as manner as described above, it was1.56.

(Formation of Color Filter)

As negative type photosensitive red material (material for R), greenmaterial (material for G) and blue material (material for B), thematerials described below were prepared.

Material for R: SR-4000L produced by Fujifilm Electronic Materials Co.,Ltd.Material for G: SG-4000L produced by Fujifilm Electronic Materials Co.,Ltd.Material for B: SB-4000L produced by Fujifilm Electronic Materials Co.,Ltd.

The materials described above were spincoated in the formation order ofG, R and B, followed by performing prebake, exposure by a ⅕ reductiontype i-line stepper, development and postbake to form a color filter(film thickness: 0.8 μm). Specifically, first, Material for G was coatedon the lower planarizing layer, and after performing prebake, exposureusing a photomask and development, postbake (220° C. for 10 minutes) wasconducted to form a green filter in a checkerboard-like pattern. Next,Material for R was coated so as to cover the green filter, and afterexposure using a photomask and development, postbake (220° C. for 10minutes) was conducted to form a red filter. Then, Material for B wascoated so as to cover the red filter and the green filter, and afterprebake, exposure using a photomask and development, postbake (220° C.for 10 minutes) was conducted to form a blue filter.

As the developer, a 50% diluted solution of CD-2000 produced by FujifilmElectronic Materials Co., Ltd. was used.

As a result of measuring the refractive index of each color filter ofthe color filter formed in the as manner as described above, therefractive index of the red filter was 1.59 (wavelength: 620 nm), therefractive index of the green filter was 1.60 (wavelength: 550 nm), andthe refractive index of the blue filter was 1.61 (wavelength: 450 nm).

(Formation of Upper Planarizing Layer)

A photocurable type acrylic transparent resin material (CT-2020Lproduced by Fujifilm Electronic Materials Co., Ltd.) was spincoated onthe color filter, followed by conducting prebake, ultraviolet ray entiresurface exposure and postbake to form an upper planarizing layer. Thethickness of the upper planarizing layer formed was 0.3 μm. Therefractive index of the upper planarizing layer measured in the asmanner as described above was 1.56.

(Formation of Microlens)

MFR401L produced by JSR Corp. was spincoated as a microlens material onthe upper planarizing layer, and prebake, exposure by a ⅕ reduction typei-line stepper, development, post exposure and melt flow by postbakewere performed to form a microlens (height: 0.657 μm). As a result ofmeasuring the refractive index of the microlens formed in the as manneras described above, it was 1.61. As the developer, 1.19% by masssolution of TMAH (tetramethylammonium hydroxide) was used.

Next, window opening of a bonding pad portion was performed.Specifically, a positive resist (positive resist for i-line PFI-27produced by Sumitomo Chemical Co., Ltd.) was spincoated, and then,prebake, exposure using a photomask having a pattern corresponding to abonding pad portion and a scribe portion, and development wereperformed. Thus, a resist pattern having apertures in the bonding padportion and the scribe portion was formed, and oxygen ashing wasperformed using the resist pattern as a mask to remove the planarizinglayer on the portion by etching. Then, the positive resist was removedusing a resist peeling liquid.

<Formation of Dye-Containing Layer 1>

A glass substrate with a dielectric multilayer film in which thedielectric multilayer film reflecting a near infrared ray (a silicalayer (SiO₂, film thickness: from 20 to 250 nm) and a titania layer(TiO₂, film thickness: from 70 to 130 nm) were alternately stacked,number of layers stacked: 44) was formed on the glass substrate at adeposition temperature of 200° C. was obtained. Each total thickness ofthe dielectric multilayer film was about 5.5 μm.

A coating film was formed on the glass substrate with a dielectricmultilayer film using each of the curable resin compositions of Examples1 to 14 according to a slit coat method (baker applicator YBA-3 Typeproduced by Yoshimitsu Seiki Co., Ltd., slit width adjusted to 250 μm),and then after performing preheating at 100° C. for 2 minutes,postheating at 140° C. for 10 minutes was conducted. A dye-containinglayer having a film thickness of about 100 μm was obtained.

The glass substrate with a dielectric multilayer film having thedye-containing layer formed was stuck on the solid-state imaging devicesubstrate obtained above using an adhesive.

Subsequently, dicing of the wafer was performed, the package assemblywas conducted to produce a solid-state imaging device according to theinvention.

<Formation of Dye-Containing Layer 2>

Further, a coating film was formed on a glass substrate using each ofthe curable resin compositions of Examples 1 to 14 according to a slitcoat method, and then after performing preheating at 100° C. for 2minutes, postheating at 140° C. for 10 minutes was conducted. Adye-containing layer having a film thickness of about 100 μm wasobtained.

A dielectric multilayer film in which the dielectric multilayer filmreflecting a near infrared ray (a silica layer (SiO₂, film thickness:from 20 to 250 nm) and a titania layer (TiO₂, film thickness: from 70 to130 nm) were alternately stacked, number of layers stacked: 44) wasformed on the surface of the dye-containing layer of the glass substratehaving the dye-containing layer formed at a deposition temperature of200° C. Each total thickness of the dielectric multilayer film was about5.5 μm.

The glass substrate having the dielectric multilayer film formed on thedye-containing layer was stuck on the solid-state imaging devicesubstrate obtained above using an adhesive.

Subsequently, dicing of the wafer was performed, the package assemblywas conducted to produce a solid-state imaging device according to theinvention.

<Evaluation of Image Sensor Chip> (Measurement and Evaluation ofIncident Angle Dependence)

A camera lens was combined with the solid-state imaging devicethus-produced, and taking sensitivity in the valid imaging region (chiefray incident angle: 0°) as 100%, relative sensitivity in each greenpixel was measured at the chief ray incident angle of 5°, 10°, 15°, 20°,25° and 30°. It was confirmed from the results that the shading wasinhibited.

Further, the improvement in the heat resistance was also confirmed byincreasing the film thickness of the dye-containing layer.

The solid-state imaging devices were obtained in the same manner asabove except that the film thicknesses of Dye-containing layer 1 andDye-containing layer 2 were changed to 60 μm, 200 μm, 250 μm and 300 μm,respectively. It was confirmed that these solid-state imaging devicesalso had sufficient near infrared ray shielding property and heatresistance. It was confirmed that the sufficient heat resistance wasobtained in the case where the film thickness was 100 μm or more, but itwas found that the image quality of the image sensor became insufficientin the case where the film thickness was 300 μm.

Example 15 Preparation of First Curable Resin Composition Having NearInfrared Ray Absorbing Property

A first curable resin composition having near infrared ray absorbingproperty was prepared by mixing the compounds described below.

(Preparation of Polymer Type Copper Sulfonate Complex X)

Water (60 parts by mass) was charged in a three-necked flask, and thetemperature was raised to 57° C. under a nitrogen atmosphere. A monomersolution (Dropping solution a) prepared by dissolving2-acrylamido-2-methylpropanesulfonic acid (100 parts by mass) in water(160 parts by weight) and an initiator solution (Dropping solution b)prepared by dissolving VA-046B (water-soluble azo-based polymerizationinitiator produced by Wako Pure Chemical Industries, Ltd., 1.164 partsby mass) in water (80 parts by mass) were prepared, and Droppingsolution a and Dropping solution b were dropwise added simultaneouslyover a period of 2 hours to be reacted. After the completion of thedropwise addition, the mixture was reacted for 2 hours, the temperaturewas raised to 65° C., and further reacted for 2 hours, thereby obtaininga 25% by mass aqueous solution of Polymer (B−1). The weight averagemolecular weight thereof was 100,000.

To the solution of (B−1) was added 0.4 equivalent of copper (II)hydroxide (18.83 parts by mass) to the acid group amount of (B−1), themixture was stirred at 50° C. for one hour and then diluted with waterto obtain a 25% by mass aqueous solution of Polymer type coppersulfonate complex X.

(Preparation of First Resin Composition Having Near Infrared RayAbsorbing Property)

Pure water (2.80 g) and dimethylformamide (1.20 g) were added to Polymertype copper sulfonate complex X (1.00 g) to obtain a first curable resincomposition. The first curable resin composition prepared was a bluetransparent liquid having a solid content concentration of 20% by mass.

<Preparation of Second Curable Resin Composition Having Near InfraredRay Absorbing Property>

A second curable resin composition having near infrared ray absorbingproperty was prepared by mixing the compounds described below.

(Synthesis of Pyrrolopyrrole dye compound (A-154))

According to the scheme shown below, Pyrrolopyrrole dye compound (A-154)was synthesized.

In 40 parts by mass of ethyl acetate were mixed 20.0 parts by mass ofIsoeicosanol (FINEOXOCOL 2000 produced by Nissan Chemical Industries,Ltd.) and 8.13 parts by mass of triethylamine, and under −10° C., 8.44parts by mass of methanesulfonyl chloride was added dropwise thereto.After the completion of the dropwise addition, the mixture was reactedat 30° C. for 2 hours. The organic phase was collected by a liquidseparation operation, and the solvent was distilled off under a reducedpressure to obtain 25.5 parts by mass of a pale yellow liquid (A-154A0form).

In 25 parts by mass of dimethylacetamide were stirred 7.82 parts by massof 4-cyanophenol and 10.1 parts by mass of potassium carbonate, 25.5parts by mass of A-154A0 form synthesized above was added thereto, andthe mixture was reacted at 100° C. for 6 hours. The organic phase wascollected by a liquid separation operation, the organic phase was washedwith an aqueous sodium hydroxide solution, and the solvent was distilledoff under a reduced pressure to obtain 25.8 parts by mass of a paleyellow liquid (A-154A form).

¹H-NMR (CDCl₃): δ 0.55-0.96 (m, 18H), 0.96-2.10 (m; 21H), 3.88 (m, 2H),6.93 (d, 2H), 7.56 (d, 2H)

Diketopyrrolopyrrole compound (A-154B form) was synthesized using 13.1parts by mass of A-154A form synthesized above as the raw material inaccordance with the method described in U.S. Pat. No. 5,969,154 toobtain 7.33 parts by mass of an orange solid (A-154B form).

¹H-NMR (CDCl₃): δ 0.55-0.96 (m, 36H), 0.96-2.10 (m; 42H), 3.95 (m, 4H),7.06 (d, 4H), 8.30 (d, 4H), 8.99 (brs, 2H)

In 30 parts by mass of toluene were stirred 7.2 parts by mass of A-154Bform and 3.42 parts by mass of 2-(2-benzothizolyl)acetonitrile, 10.0parts by mass of phosphorus oxychloride was added thereto, and themixture was refluxed by heating for 5 hours. The organic phase wascollected by a liquid separation operation and washed with an aqueoussodium hydrogen carbonate solution, and the solvent was distilled offunder a reduced pressure.

The crude product was purified by silica gel column chromatography(solvent: chloroform), and further recrystallized from achloroform/acetonitrile solvent to obtain 5.73 parts by mass of a greensolid (A-154D form).

¹H-NMR (CDCl₃): δ 0.55-1.00 (m, 36H), 1.00-2.10 (m; 42H), 3.97 (m, 4H),7.11 (d, 4H), 7.28 (t, 2H), 7.43 (t, 2H), 7.67-7.75 (m, 6H), 7.80 (d,2H), 13.16 (s, 2H)

In 70 parts by mass of toluene was stirred 2.53 parts by mass of2-aminoethyl diphenylborinate at 40° C., 3.56 parts by mass of titaniumchloride was added thereto, and the mixture was reacted for 30 minutes.Then, 5.60 parts by mass of A-154D form was added thereto, and themixture was refluxed by heating at an external temperature of 130° C.for one hour. The mixture was cooled to room temperature, 80 parts bymass of methanol was added thereto to deposit crystals, and the crystalswere collected by filtration. The crude crystals obtained were purifiedby silica gel column chromatography (solvent: chloroform), and furtherrecrystallized from a toluene/methanol solvent to obtain 3.87 parts bymass of the desired compound (A-154) as green crystals.

The λmax of Compound (A-154) was 780 nm in chloroform. The molarabsorption coefficient thereof was 2.21×10⁵ dm³/mol·cm in chloroform.

¹H-NMR (CDCl₃): δ 0.55-1.01 (m, 36H), 1.01-2.10 (m; 42H), 3.82 (m, 4H),6.46 (s, 8H), 6.90-7.05 (m, 6H), 7.07-7.19 (m, 12H), 7.21-7.29 (m, 8H),7.32 (d, 2H)

(Synthesis of Polymerizable Compound (Resin (B−1)))

Under a nitrogen atmosphere, 33.26 parts by mass of cyclohexanone washeated to 85° C. A mixed solution of 22.36 parts by mass of glycidylmethacrylate, 12.38 parts by mass of 1,1,1,3,3,3-hexafluoroisopropylmethacrylate, 33.26 parts by mass of cyclohexanone and 1.45 parts bymass of dimethyl 2,2′-azobisisobutyrate (V-601 produced by Wako PureChemical Industries, Ltd.) was added dropwise thereto with stirring overa period of 2 hours. After the completion of the dropwise addition, themixture was stirred further at 85° C. for 2 hours and further 90° C. for2 hours to obtain Resin (B−1). The weight average molecular weight (Mw:calculated in terms of polystyrene) of the resin obtained determined byGPC (carrier: tetrahydrofuran (THF)) was 13,300, and a degree ofdispersion (Mw/Mn) was 2.26.

(Second Curable Resin Composition Having Near Infrared Ray AbsorbingProperty)

A second curable resin composition having near infrared ray absorbingproperty was prepared by mixing the components described below.

Pyrrolopyrrole dye compound (A-154) 2.40 parts by mass Polymerizablecompound: Resin (B-1) 6.80 parts by mass Polymerizable compound: EHPE3150 (produced 14.5 parts by mass by Daicel Chemical Industries, Ltd.)Curing agent: Pyromellitic anhydride 3.50 parts by mass Polymerizationinhibitor: p-Methoxyphenol 0.10 parts by mass Solvent: Cyclohexanone72.65 parts by mass Surfactant: MEGAFAC F-781-F (produced by 0.05 partsby mass DIC Corp.)

<Formation of Near Infrared Ray Cut Filter>

A near infrared ray cut filter was produced in the method describedbelow using the first curable resin composition having near infrared rayabsorbing property and the second curable resin composition having nearinfrared ray absorbing property prepared.

The second curable resin composition having near infrared ray absorbingproperty was coated (2,000 rpm, 20 seconds) by spin coat (using SpinCoater 1H-D7 produced by Mikasa Co., Ltd.) on a glass substrate, andprebaked at 100° C. for 2 minutes and postbaked at 230° C. for 5 minutesby a hot plate. The first curable resin composition having near infraredray absorbing property was coated thereon by an applicator coatingmethod (slit width: 400 μm), and prebaked at 100° C. for 30 minutes andpostbaked at 120° C. for 15 minutes in an oven, thereby producing a nearinfrared ray cut filter. The film thickness of the near infrared ray cutfilter obtained was 148.4 μm. The film thickness of layer formed by thesecond curable resin composition was 1.2 μm.

<Evaluation of Near Infrared Ray Shielding Property>

A spectral transmittance of the near infrared ray cut filter obtained asdescribed above was measured by using a spectrophotometer U-4100(produced by Hitachi High-Technologies Corp.). It was confirmed from theresults that the near infrared ray cut filter which sufficientlyshielded light in the near infrared region and in which the incidentangle dependence was reduced was able to be provided.

Example 16 Synthesis of Pyrrolopyrrole Dye and Production of AqueousDispersion of the Same (Preparation of Pyrrolopyrrole Dye Compound(D-17))

Pyrrolopyrrole dye compound (D-17) was prepared according to Scheme 1shown below in the same manner as in Synthesis Example 1 of the exampleof JP-A-2011-68731.

¹H-NMR (CDCl₃): δ 0.9-1.0 (m, 12H), 1.35-1.6 (m; 16H), 1.8 (m, 2H), 3.95(d, 4H), 7.1 (d, 4H), 7.4-7.5 (m, 4H), 7.7 (d, 4H), 7.75 (d, 2H), 8.0(d, 2H)

(Preparation of Pyrrolopyrrole Dye Compound (D-10))

Pyrrolopyrrole dye compound (D-10) was prepared according to Scheme 1described above in the same manner as in Synthesis Example 2 of theexample of JP-A-2011-68731.

The λmax of Compound (D-10) was 779 nm in chloroform. The molarabsorption coefficient thereof was 2.06×10⁵ dm³/mol·cm in chloroform.

¹H-NMR (CDCl₃): δ 0.9-1.0 (m, 12H), 1.35-1.6 (m; 16H), 1.8 (m, 2H), 3.85(d, 4H), 6.45 (s, 8H), 7.0 (d, 4H), 7.15 (m, 12H), 7.2 (m, 2H), 7.25 (m,4H+4H), 7.5 (m, 2H)

(Preparation of Pyrrolopyrrole Dye Compound (D-141A))

Pyrrolopyrrole dye compound (D-141A) described below was prepared in thesame manner as Pyrrolopyrrole dye compound (D-10) except for changingthe starting material.

(Production of Aqueous Dispersion of Pyrrolopyrrole Dye Fine Particle)

To any one kind of the pyrrolopyrrole dye compounds described above (6parts by mass) and a dispersing agent (DISPERBYK 191 produced by BYKChemie GmbH (4 parts by mass) was added a dispersion medium (water (90parts by mass)) to make 100 parts by mass. Further, 100 parts by mass ofzirconia beads of 0.1 mmφ was added thereto, and the mixture was treatedby a planetary ball mill at 300 rpm for 8 hours. The beads wereseparated by filtration to produce an aqueous dispersion ofpyrrolopyrrole dye fine particle composed of fine particles.

<Preparation of Curable Resin Composition Having Near Infrared RayAbsorbing Property>

A curable resin composition having near infrared ray absorbing propertywas prepared by mixing the compounds described below.

To a copper complex having a sulfonic acid as a ligand represented byA-1 shown below (2.50 g) were added a 50% by mass aqueous solution ofpolyacrylamide (AQ Nylon A-90 produced by Toray Industries, Inc.) (5.00g) and the aqueous dispersion of pyrrolopyrrole dye fine particledescribed above (2.50 g) to obtain a curable resin composition havingnear infrared ray absorbing property having copper sulfonatecomplex:pyrrolopyrrole dye fine particle:other solid content=50:3:52 anda solid content concentration of 52.5% by mass. The curable resincomposition having near infrared ray absorbing property prepared was ablue transparent liquid.

TABLE 2

Sulfonic acid R A-1 —CH₃ A-2 —CF₃ A-3

A-4

<Production of Near Infrared Ray Cut Filter>

The composition having near infrared ray absorbing property prepared inExample 16 was coated on a glass substrate using an applicator coatingmethod (baker applicator YBA-3 Type produced by Yoshimitsu Seiki Co.,Ltd., slit width adjusted to 250 μm, 400 μm), prebaked in an oven at100° C. for 30 minutes, and further postbaked in an oven at 120° C. for15 minutes, thereby producing a near infrared ray cut filter. The filmthickness of the near infrared ray cut filter obtained was 151.5 μm.

<Evaluation of Near Infrared Ray Shielding Property>

A spectral transmittance of the near infrared ray cut filter obtained asdescribed above was measured by using a spectrophotometer U-4100(produced by Hitachi High-Technologies Corp.). It was confirmed from theresults that the near infrared ray cut filter which sufficientlyshielded light in the near infrared region and in which the incidentangle dependence was reduced was able to be provided.

Near infrared ray cut filters were obtained in the same manner as inExamples 15 and 16 except that the film thickness of the coppercomplex-containing layer in Examples 15 and 16 was changed to 60 μm, 100μm, 200 μm and 250 μm, respectively. It was confirmed that theseinfrared ray cut filters also had the sufficient near infrared rayshielding property.

Near infrared ray cut filters were produced in the same manner as inExample 16 except that Sulfonic acid A-1 in Example 16 was changed toSulfonic acids A-2 to A-4, respectively. Further, a near infrared raycut filter was produced in the same manner as in Example 16 except thatPyrrolopyrrole dye D-10 in Example 16 was changed to Pyrrolopyrrole dyeD-141A. It was confirmed that these near infrared ray cut filters werealso able to provide the near infrared ray cut filter which sufficientlyshielded light in the near infrared region and in which the incidentangle dependence was reduced. In these examples, by adding thepyrrolopyrrole dye, the near infrared ray absorbing ability in thevicinity of the maximum absorption wavelength of the dye was able to befurther increased.

INDUSTRIAL APPLICABILITY

According to the invention, a curable resin composition capable ofproducing an image sensor chip in which the color shading is suppressedcan be provided.

Also, a curable resin composition which can produce an image sensor chipin which a stack functioning as an infrared ray cut filter andincluding, for example, a dye-containing layer and an infrared rayreflecting film and a surface of a solid-state imaging device substrateare closely contacted with each other without a space and by which theincident angle dependence of light received can be suppressed, aproduction method of image sensor chip using the same, and an imagesensor chip can be provided.

Although the invention has been described in detail and by reference tospecific embodiments, it is apparent to those skilled in the art that itis possible to add various alterations and modifications insofar as thealterations and modifications do not deviate from the spirit and thescope of the invention.

This application is based on a Japanese patent application filed on Nov.30, 2012 (Japanese Patent Application No. 2012-263644), and the contentsthereof are incorporated herein by reference.

DESCRIPTION OF REFERENCE NUMERALS AND SIGNS

-   10: Silicon substrate-   12: Imaging device-   13: Interlayer insulating film-   14: Base layer-   15: Color filter-   16: Overcoat-   17: High refractive index layer-   18: Light-shielding film-   20: Adhesive-   22: Insulating film-   23: Metal electrode-   24: Solder resist layer-   26: Internal electrode-   27: Device surface electrode-   30: Glass substrate-   35: Infrared ray reflecting film-   40: Imaging lens-   42: Dye-containing layer-   44: Light-shielding and electromagnetic shield-   45: Adhesive-   46: Low refractive index layer-   50: Lens holder-   60: Solder ball-   70: Circuit board-   100: Solid-state imaging device substrate-   200: Camera module

1. A curable resin composition which is capable of being coated so as tohave a film thickness of 20 μm or more and contains a dye having amaximum absorption wavelength in a wavelength range from 600 to 850 nm.2. The curable resin composition as claimed in claim 1, wherein the dyeis at least one kind selected from the group consisting of apyrrolopyrrole dye, a copper complex, a cyanine-based dye, aphthalocyanine-based dye, a quaterrylene-based dye, an aminium-baseddye, an imminium-based dye, an azo-based dye, an anthraquinone-baseddye, a diimonium-based dye, a squarylium-based dye and a porphyrin-baseddye.
 3. The curable resin composition as claimed in claim 1, wherein thedye is a pyrrolopyrrole dye or a copper complex.
 4. The curable resincomposition as claimed in claim 1, which has a solid contentconcentration from 10 to 90% by mass and a viscosity at 25° C. from 1mPa·s to 1,000 Pa·s.
 5. The curable resin composition as claimed inclaim 1, which further contains a polymerizable compound and a solvent,and a content of the dye in a total solid content of the composition is30% by mass or more.
 6. A curable resin composition which contains a dyehaving a maximum absorption wavelength in a wavelength range from 600 to850 nm and has a solid content concentration from 10 to 90% by mass anda viscosity at 25° C. from 1 mPa·s to 1,000 Pa·s.
 7. An infrared ray cutfilter having a dye-containing layer having a film thickness of 20 μm ormore formed from the curable resin composition as claimed in claim
 1. 8.An infrared ray cut filter having a first dye-containing layercontaining a copper complex and a second dye-containing layer containinga pyrrolopyrrole dye.
 9. The infrared ray cut filter as claimed in claim8, wherein a film thickness of the first dye-containing layer is 50 μmor more and a film thickness of the second dye-containing layer is 5 μmor less.
 10. A production method of image sensor chip comprising a stepof coating the curable resin composition as claimed in claim 1 on aglass substrate to form a dye-containing layer, and a step of adheringthe glass plate having the dye-containing layer formed on a solid-stateimaging device substrate.
 11. The production method of image sensor chipas claimed in claim 10, wherein the coating of the curable resincomposition is applicator coating and the applicator coating isperformed by setting a solid content concentration and a viscosity ofthe curable resin composition to from 40 to 70% by mass and 300 to 700mPa·s, respectively.
 12. The production method of image sensor chip asclaimed in claim 10, wherein the glass substrate further has an infraredray reflecting film, and (1) a surface of the glass substrate on whichthe infrared ray reflecting film is formed is adhered on the solid-stateimaging device substrate or (2) a surface of the glass substrate onwhich the infrared ray reflecting film is not formed is adhered on thesolid-state imaging device substrate.
 13. The production method of imagesensor chip as claimed in claim 10, wherein the glass substrate furtherhas an antireflection film.
 14. The production method of image sensorchip as claimed in claim 13, wherein the infrared ray reflecting film ispresent on one surface of the glass substrate and the antireflectionfilm is present on the other surface of the glass substrate.
 15. Theproduction method of image sensor chip as claimed in claim 12, whereinthe infrared ray reflecting film is a dielectric multilayer film. 16.The production method of image sensor chip as claimed in claim 10,wherein the solid-state imaging device substrate has a color filterlayer, a high refractive index layer and a low refractive index layer.17. An image sensor chip comprising a solid-state imaging devicesubstrate, a dye-containing layer composed of the curable resincomposition as claimed in claim 1 and a glass substrate having aninfrared ray reflecting film, wherein these are closely contacted witheach other without intervention of an air layer.
 18. The image sensorchip as claimed in claim 17, wherein the infrared ray reflecting film isprovided on a surface of the glass substrate opposed to thedye-containing layer composed of the curable resin composition.
 19. Theimage sensor chip as claimed in claim 17, wherein the dye-containinglayer is provided between the infrared ray reflecting film and the glasssubstrate.
 20. The image sensor chip as claimed in claim 17, wherein anantireflection film is further provided on an outermost surface of theimage sensor chip comprising the solid-state imaging device substrate,the dye-containing layer and the infrared ray reflecting film.